Coated glass article

Abstract

Described herein is a coated glass article comprising a glass substrate comprising a first major surface and a second major surface. The first major surface and the second major surface may be opposite sides of the glass substrate. The coated glass article includes an optical coating disposed on the first major surface of the glass substrate. The coated glass article may have a retention strength after impact damage of greater than or equal to 250 MPa. The failure height of the coated glass article can be greater than or equal to 50 cm as measured on No.80 sandpaper according to the drop test method. In addition, the substrate may include 5.0 to 10.0 mol% Li2O, 1.0 to 10.0 mol% Na2O, and a molar ratio of lithium to sodium (Li2O: Na2O) of 1.2 to 2.0.

Description

[0001] Priority Declaration

[0002] This application claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Application No. 63 / 452,727, filed on March 17, 2023, and claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Application No. 63 / 430,186, filed on December 5, 2022. The entire contents of each of these applications are hereby incorporated herein by reference for all purposes. Technical Field

[0003] The present disclosure relates to coated articles, and more particularly, to coated glass articles suitable for use as covers, user interfaces, and / or displays for electronic device products (eg, mobile devices). Background Art

[0004] Cover products are often used to protect key devices within electronic products, provide user interfaces for input and / or display, and / or many other functions. Such products include mobile devices such as smartphones, MP3 players, and tablet computers. Cover products also include architectural products, transportation products (e.g., products for automotive applications, trains, aircraft, marine vessels, etc.), electrical products, or any product requiring a certain degree of transparency, scratch resistance, abrasion resistance, or a combination thereof.

[0005] These applications typically require a combination of scratch resistance, drop performance, and retention after surface damage, along with strong optical performance characteristics. Optical performance can be measured in terms of maximum light transmission and minimum reflectivity.

[0006] Typically, coatings applied to glass substrates to enhance optical properties (e.g., increased transmittance and / or reduced reflectivity) and / or scratch resistance can reduce the mechanical properties (e.g., drop resistance and / or retained strength after surface damage) of cover articles incorporating these features. Generally, state-of-the-art cover articles do not meet all combinations of these requirements, or at least can be improved. Summary of the Invention

[0007] The present disclosure discloses coated articles that meet the aforementioned requirements of scratch resistance, drop performance, retained strength after surface damage, and robust optical performance characteristics (eg, in terms of maximum light transmission and minimum reflectivity).

[0008] According to one or more embodiments of the present disclosure, a coated glass article may include a glass substrate comprising a first major surface and a second major surface. The first major surface and the second major surface may be opposite sides of the glass substrate. The composition of the glass substrate may include: SiO2 in an amount greater than or equal to 50.0 mol% and less than or equal to 70.0 mol%; Al2O3 in an amount greater than or equal to 10.0 mol% and less than or equal to 20.0 mol%; P2O5 in an amount greater than or equal to 0.0 mol% and less than or equal to 2.0 mol%; B2O3 in an amount greater than or equal to 1.0 mol% and less than or equal to 6.0 mol%; Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 10.0 mol%; and K2O in an amount greater than or equal to 0.01 mol% and less than or equal to 1.0 mol%. The coated glass article may also include an optical coating disposed on the first major surface of the glass substrate. The optical coating may form an antireflective surface. The optical coating may include a scratch-resistant layer and an antireflective coating, the antireflective coating comprising a plurality of alternating high and low refractive index layers disposed between the scratch-resistant layer and the glass substrate. The physical thickness of the optical coating may be from about 50 nm to about 10 microns. The coated glass article may exhibit a maximum hardness of from about 10 GPa to about 30 GPa, measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, as measured by the Berkovich Indenter Hardness Test. The coated glass article may exhibit a retained strength greater than or equal to 250 MPa. Therefore, these coated glass article embodiments may be used in a variety of electronic device products and may provide a favorable combination of scratch resistance, drop performance, retained strength after surface damage, and strong optical performance characteristics (e.g., increased transmittance and reduced reflectivity).

[0009] According to other embodiments of the present disclosure, a coated glass article for a mobile display cover may include a glass substrate having a composition including: SiO2 in an amount greater than or equal to 50.0 mol% and less than or equal to 70.0 mol%; Al2O3 in an amount greater than or equal to 10.0 mol% and less than or equal to 25.0 mol%; and Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 15.0 mol%. The glass substrate may include a first major surface and a second major surface. The first major surface and the second major surface may be opposite sides of the glass substrate. The glass substrate may also include a layer depth greater than or equal to 3 μm. The glass substrate may also include an elastic modulus greater than or equal to 72 GPa. The glass substrate may also include a strength greater than or equal to 0.7 MPa·m 0.5 The glass substrate may further comprise an optical coating disposed on the first major surface of the glass substrate. The coated glass article may exhibit an average clear visual transmittance greater than 85% and an average clear visual reflectance less than 8%. The coated glass article may exhibit a maximum hardness of about 12 GPa to about 30 GP measured at an indentation depth of about 600 nm from the anti-reflective surface of the optical coating, the maximum hardness being measured by a Bosch indenter hardness test. The coated glass article may also exhibit a retained strength greater than or equal to 250 MPa. Therefore, these coated glass article embodiments can be used in various electronic device products and can provide an advantageous combination of scratch resistance, drop performance, retained strength after surface damage, and strong optical performance characteristics (e.g., increased transmittance and reduced reflectivity).

[0010] According to yet other embodiments of the present disclosure, a coated glass article may include a glass substrate comprising a first major surface and a second major surface, wherein the first major surface and the second major surface are opposite sides of the glass substrate. The coated glass article may include an optical coating disposed on the first major surface of the glass substrate, the optical coating forming an antireflective surface, wherein the optical coating comprises a scratch-resistant layer and an antireflective coating, the antireflective coating comprising a plurality of alternating high and low refractive index layers disposed between the scratch-resistant layer and the glass substrate. The optical coating has a physical thickness of about 50 nm to about 10 microns. The coated glass article exhibits a maximum hardness of about 10 GPa to about 30 GPa measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, as measured by a Bosch indenter hardness test. The coated glass article has a failure height of about 50 cm to about 220 cm measured on 80 grit garnet sandpaper according to a drop test method. Thus, these cover article embodiments may be used in a variety of electronic device products and may provide a favorable combination of scratch resistance, drop performance, retained strength after surface damage, and strong optical performance characteristics (eg, increased transmittance and reduced reflectivity).

[0011] Additional features and advantages will be set forth in the detailed description that follows, and in part will be apparent to those skilled in the art from that description or will be learned by practicing the embodiments described herein, including the detailed description that follows, the claims, and the accompanying drawings.

[0012] It should be understood that both the foregoing general description and the following detailed description are merely exemplary and are intended to provide an overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding and are incorporated into and constitute a part of this specification. The drawings illustrate one or more embodiments and, together with the description, serve to explain the principles and operation of the various embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1A is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0014] Figure 1B is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0015] Figure 2 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0016] Figure 3is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0017] Figure 4 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0018] Figure 5 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0019] Figure 6 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0020] Figure 7 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0021] Figure 8 is a cross-sectional side view of a coated article according to one or more embodiments described herein;

[0022] Figure 9 is a graph of optical coating thickness scaling factor versus portion of surface curvature for a deposition process according to one or more embodiments described herein;

[0023] Figure 10A is a plan view of an exemplary electronic device incorporating any of the coated articles described herein;

[0024] Figure 10B According to one or more embodiments described herein Figure 10A A perspective view of an exemplary electronic device;

[0025] Figure 11 is a plan view of an exemplary apparatus drop machine that may be used to perform drop test methods according to one or more embodiments described herein;

[0026] Figure 12 yes Figure 11 a plan view of a machine in which the chuck of the device dropper is released, the chuck jaws are opened, and the test puck is released;

[0027] Figure 13 yes Figure 11 a plan view of a machine in which a falling test mass strikes a falling surface;

[0028] Figure 14 is a schematic diagram of an apparatus for causing damage to a glass article by impact with an impacting object according to one or more embodiments described herein;

[0029] Figure 15is a boxplot of failure heights of example glazings and comparative glazings according to one or more embodiments described herein;

[0030] Figure 16 According to one or more embodiments described herein Figure 15 a plot of example glazing failure heights versus comparison glazing failure heights, including all raw failure height data;

[0031] Figure 17 is a box plot of failure stresses of example glass articles according to one or more embodiments described herein and failure stresses of comparative glass articles;

[0032] Figure 18 According to one or more embodiments described herein Figure 17 A plot of the failure stress of an example glass product versus the failure stress of a comparison glass product, including all raw failure stress data;

[0033] Figure 19 is an image of an exemplary apparatus drop machine that may be used to perform drop testing methods according to one or more embodiments described herein;

[0034] Figure 20 is a cross-section of a simulated mobile handheld device that may be used to perform a drop test method according to one or more embodiments described herein;

[0035] Figure 21 is another view of a simulated mobile handheld device that may be used to perform a drop test method according to one or more embodiments described herein;

[0036] Figure 22 is a schematic diagram of a face of a simulated mobile handheld device that can be used to perform a drop test method according to one or more embodiments described herein;

[0037] Figure 23 is an image of an exemplary simulated mobile handheld device that may be used to perform a drop test method according to one or more embodiments described herein;

[0038] Figure 24 is an image of an exemplary drop surface that may be used to perform a drop test method according to one or more embodiments described herein;

[0039] Figure 25 is another schematic diagram of an apparatus for causing damage to a glass article by impact of an impacting object according to one or more embodiments described herein;

[0040] Figure 26is an image showing preparation of an impact object of an apparatus for causing damage to a glass article by impact of the impact object according to one or more embodiments described herein;

[0041] Figure 27 is an image of the preparation of a glass article for use with an apparatus for causing damage to the glass article by impact of an impacting object according to one or more embodiments described herein;

[0042] Figure 28 is an image of a glass article positioned in an apparatus for causing damage to the glass article by the impact of an impacting object according to one or more embodiments described herein;

[0043] Figure 29 is a schematic diagram of a test apparatus for a 4-point bend test according to one or more embodiments described herein; and

[0044] Figure 30 is an image of an exemplary 4-point bend test apparatus according to one or more embodiments described herein. DETAILED DESCRIPTION

[0045] Reference will now be made in detail to various embodiments of coated glass articles, examples of which are illustrated in the accompanying drawings. The embodiments disclosed herein may include glass substrates having optical coatings. Furthermore, the coated glass articles are suitable for use as cover articles, user interfaces, and / or displays for electronic device products (e.g., mobile devices). As described herein, due to the combination of specific optical coatings on specific glass substrates, the coated glass articles may have enhanced optical characteristics as well as enhanced mechanical characteristics. According to one or more embodiments, the use of these specific optical coatings in combination with these specific glass substrates may provide a synergistic enhancement compared to comparable products known in the art. Furthermore, the coated glass articles, cover articles, user interfaces, and / or displays of the present disclosure may be used in combination with screen protectors having optical coatings, as disclosed in U.S. Provisional Patent Application No. _____, entitled “Screen Protectors Tailored for Electronic Device Displays” (Docket No. SP23-060PZ), filed by _____, the contents of which are hereby incorporated herein by reference.

[0046] In addition, the coated glass articles of the present disclosure exhibit a combination of scratch resistance, drop performance, retained strength after surface damage, and strong optical performance characteristics. The optical performance can be measured based on maximum light transmittance and minimum reflectance. Generally speaking, the coated glass articles of the present disclosure have a glass substrate comprising a first major surface and a second major surface opposite the first major surface. These coated glass articles further include an optical coating disposed on the first major surface of the glass substrate. The coated glass articles can have a retained strength after impact damage greater than or equal to 250 MPa. The coated glass articles can have a failure height greater than or equal to 50 cm as measured on 80 grit sandpaper according to the drop test method. In addition, the substrate can comprise a glass composition having 5.0-10.0 mol% Li2O, 1.0-10.0 mol% Na2O, and a lithium to sodium molar ratio (Li2O:Na2O) of 1.2 to 2.0. In some implementations, the coated glass articles of the present disclosure utilize substrates having glass compositions that are substantially free of Ta2O5, HfO2, La2O3, and Y2O3. Ultimately, the composition selected for the glass substrate of the coated articles of the present disclosure can improve the article's drop performance and retained strength after surface damage, while enabling the use of coatings that can provide other described performance attributes (e.g., scratch resistance, high transmittance, and low reflectivity).

[0047] See Figure 1A and 1B According to one or more embodiments disclosed herein, a coated glass article 100 may include a glass substrate 110 and an optical coating 120 disposed on the substrate. The glass substrate 110 may include opposing major surfaces 112, 114 and opposing minor surfaces 116, 118. The optical coating 120 may be Figure 1A and 1B 1. The optical coating 120 is shown disposed on the first opposing major surface 112; however, in addition to or instead of being disposed on the first opposing major surface 112, the optical coating 120 may be disposed on the second opposing major surface 114 and / or one or both opposing minor surfaces. As depicted, the second major surface 114 may be planar. In other embodiments, the second major surface 114 may be non-planar. The optical coating 120 forms an anti-reflective surface 122. The anti-reflective surface 122 forms an air interface and generally defines the edge of the optical coating 120 and the entire coated glass article 100. As described herein, the glass substrate 110 may be substantially transparent.

[0048] According to one or more embodiments described herein, the glass substrate 110 may be planar. As used herein, a planar substrate refers to a substrate whose major surfaces 112, 114 of the glass substrate 110 are geometrically flat. For example, Figure 1BAs shown, major surfaces 112 and 114 may comprise flat geometries.

[0049] According to one or more embodiments described herein, the glass substrate 110 may be non-planar. As used herein, a non-planar substrate refers to a substrate in which at least one of the major surfaces 112, 114 of the glass substrate 110 is not geometrically flat. For example, Figure 1A As shown, a portion of the first major surface 112 may include a curved geometry. The degree of curvature of the first major surface 112 may vary. For example, an embodiment may have a curvature measured by an approximate radius of about 1 mm to several meters (i.e., approximately planar), such as about 3 mm to about 30 mm, or about 5 mm to about 10 mm. In an embodiment, a non-planar substrate may include a planar portion, such as Figure 1A As shown. For example, a touch screen of a portable electronic device may include a substantially planar surface at or near its center and curved (i.e., non-planar) portions around its edges. Examples of such substrates include the cover glass of an Apple iPhone 6 smartphone or a Samsung Galaxy S6 Edge smartphone. While some embodiments of non-planar substrates are depicted, it should be understood that non-planar substrates can take on a variety of shapes, such as curved sheets, multi-faceted sheets, sheets with angular surfaces, or even tubular sheets.

[0050] In another embodiment, when glass substrate 110 is non-planar, glass substrate 110 includes a first major surface 112 including at least two portions, namely, a first portion 113 and a second portion 115, which are non-planar relative to each other (i.e., portions 113 and 115 are not in the same plane or otherwise parallel to each other). According to some embodiments, second portion 115 has a curved or multi-faceted shape. Direction n1 is perpendicular to first portion 113 of first major surface 112, and direction n2 is perpendicular to second portion 115 at position 115A of first major surface 112. In embodiments, the angle between n1 and n2 may be at least about 5 degrees, at least about 10 degrees, at least about 15 degrees, at least about 20 degrees, at least about 25 degrees, at least about 30 degrees, at least about 35 degrees, at least about 40 degrees, at least about 45 degrees, at least about 50 degrees, at least about 55 degrees, at least about 60 degrees, at least about 70 degrees, at least about 80 degrees, at least about 90 degrees, at least about 120 degrees, at least about 150 degrees, or even at least about 180 degrees (e.g., for a tubular substrate, the angle between n1 and n2 may be 180 degrees). For example, the angle between n1 and n2 may be in the range of about 10 degrees to about 30 degrees, about 10 degrees to about 45 degrees, about 10 degrees to about 60 degrees, about 10 degrees to about 75 degrees, about 10 degrees to about 90 degrees, about 10 degrees to about 120 degrees, about 10 degrees to about 150 degrees, or about 10 degrees to about 180 degrees. In additional embodiments, the angle between n1 and n2 (and / or n3) may be in the following range: about 10 degrees to about 80 degrees, about 20 degrees to about 80 degrees, about 30 degrees to about 80 degrees, about 40 degrees to about 80 degrees, about 50 degrees to about 80 degrees, about 60 degrees to about 80 degrees, about 70 degrees to about 80 degrees, about 20 degrees to about 180 degrees, about 30 degrees to about 180 degrees, about 40 degrees to about 180 degrees, about 50 degrees to about 180 degrees, about 60 degrees to about 180 degrees, about 70 degrees to about 150 degrees, or about 80 degrees to about 180 degrees.

[0051] Light transmitted through or reflected by the coated glass article 100 can be measured in the viewing direction v (ie, v1 for n1 and v2 for n2) as Figure 1A and 1B As shown, the direction may not be perpendicular to the first major surface 112 of the glass substrate 110. The viewing direction may be referred to as the incident illumination angle measured from the normal direction at each surface. For example, and as will be explained herein, reflected color, transmitted color, average light reflectance, average light transmittance, photopic reflectance, and photopic transmittance. The viewing direction v defines an incident illumination angle θ, which is the angle between a direction n perpendicular to the substrate surface and the viewing direction v (i.e., θ1 is the incident illumination angle between the normal direction n1 and the viewing direction v1, and θ2 is the incident illumination angle between the normal direction n2 and the viewing direction v2). It should be understood that although Figure 1A and 1BIncident illumination angles other than 0 degrees are depicted, but in some embodiments, the incident illumination angle may be equal to about 0 degrees, such that v is equal to n. When the incident illumination angle θ is varied, the optical properties of a portion of the coated glass article 100 may vary.

[0052] As used herein, "transmittance color" and "reflection color" refer to the color of a transparent article of the present disclosure as transmitted or reflected in terms of color in the CIE L*, a*, b* colorimetric system under a D65 illuminant. More specifically, "transmittance color" and "reflection color" are given by √(a* 2 +b* 2 ) because these color coordinates are measured with a D65 illuminant in transmission or reflection through the major surface of the transparent article substrate over a range of incident angles (e.g., 0 degrees to 10 degrees).

[0053] In one or more embodiments, a single layer or multiple layers of the optical coating 120 may be deposited onto the glass substrate 110 by a vacuum deposition technique, such as, for example, chemical vapor deposition (e.g., plasma-enhanced chemical vapor deposition (PECVD), low-pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, and plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (PVD) (e.g., reactive or non-reactive sputtering or laser ablation), thermal evaporation or electron beam evaporation, and / or atomic layer deposition. Liquid-based methods such as spraying, dipping, spin coating, or slot coating (e.g., using sol-gel materials) may also be used. In some embodiments, PVD techniques that rely on "metal mode" reactive sputtering may be employed, wherein a thin layer of metal is deposited in one portion of a deposition chamber and the film is reacted with a gas, such as oxygen or nitrogen, in a different portion of the deposition chamber. In some embodiments, PVD techniques that rely on "in-line" reactive sputtering may be employed, wherein material deposition and reaction occur in the same portion of the deposition chamber. In general, vapor deposition techniques may include a variety of vacuum deposition methods that can be used to produce thin films. For example, physical vapor deposition uses a physical process (such as heating or sputtering) to generate a material vapor, which is then deposited on the coated object. These deposition processes, particularly PVD methods, may have a "line of sight" characteristic, where the deposited material moves in a uniform direction during deposition onto the substrate, regardless of the angle between the deposition direction and the normal to the substrate surface.

[0054] See Figure 1A In some embodiments, the thickness of the optical coating 120 disposed on the first major surface 112 measured in a direction perpendicular to the substrate may be different between portions of the optical coating 120 disposed over the first portion 113 and the second portion 115 of the glass substrate 110. Figure 1A ,Arrow d shows the line-of-sight deposition direction. Figure 1AThe deposition direction d in FIG. 1 is perpendicular to the second major surface 114 of the glass substrate 110, such as may be common in systems where the substrate rests on the second major surface 114 during deposition of the optical coating 120. The arrow of line d points in the direction of line-of-sight deposition. Line t shows the direction perpendicular to the first major surface 112 of the glass substrate 110. The normal thickness of the optical coating 120 measured in the direction perpendicular to the first major surface 112 is represented by the length of line t. Deposition Angle is defined as the angle between the deposition direction d and the direction perpendicular to the first major surface 112 (i.e., line t). If the optical coating 120 is deposited with line-of-sight deposition characteristics, then for some vapor deposition processes, it is observed that the thickness of a portion of the optical coating 120 generally follows The square root of the cosine of Figure 9 and corresponding descriptions). Therefore, with As the cosine increases, the thickness of the optical coating 120 decreases. Although the actual thickness of the optical coating 120 deposited by vapor deposition may be different from the cosine The thickness determined by the scalar of the square root of is different, but it provides an estimate that can be used to model optical coating designs that may have good performance when applied to a non-planar glass substrate 110. In addition, although Figure 1A n1 and d in the same direction, but they need not be in the same direction in all embodiments. Without being bound by theory, it has also been observed that the physical vapor deposition process of the present disclosure does not always follow a completely line-of-sight characteristic due to the complex interactions between the sputtered atoms and molecules as they move from the sputtering target to the glass substrate 110 during sputtering plasma deposition. Nevertheless, one can adjust the physical vapor deposition process to achieve The square root of the cosine of Figure 9 and corresponding description), which can then be advantageously used to configure the structure of the optical coating 120 to have desired optical and mechanical properties at both the first portion 113 and the second portion 115.

[0055] It should be understood that throughout this disclosure, unless otherwise stated, the thickness of the optical coating 120 is measured in the normal direction n. In embodiments where the glass substrate 110 is non-planar, the coating thickness over the first portion 113 may be thicker than the coating thickness over the second portion 115, based on the line-of-sight coating scheme for the first portion 113. This thickness difference can be described by a "scaling factor," which is the difference in coating thickness between the two portions 113, 115. For example, and as described herein, a scaling factor of 0.5 corresponds to an embodiment where the coating thickness at the second portion 115 is 50% of the coating thickness at the first portion 113, where both thicknesses are measured perpendicular to the normal direction n. In some embodiments, when the glass substrate 110 is non-planar, the coating thickness can be uniform across the entire surface of the glass substrate 110.

[0056] Embodiments of the present disclosure also include coated glass articles 100 (see Figures 1-8) having a range of partial surface angles (partial surface curvatures), including coated articles without surface curvature, combined with an optical coating 120 designed to withstand coating thinning caused by various coating deposition processes. The end result is a coated glass article 100 having a range of partial surface curvature angles, wherein the optical coating 120 has controlled hardness, reflectivity, color, and color shift with viewing angle over the entire surface of the coated glass article 100, including over some or all of the curved region (e.g., at the second portion 115). In addition to meeting certain target absolute levels of hardness, reflectivity, and color, the coated glass article 100 can also exhibit smaller variations in these values, particularly smaller variations in visible light reflectivity and color, when the thickness of the optical coating 120 is reduced by a scaling factor corresponding to the actual reduction in coating thickness that occurs when performing an industrially scalable reactive sputtering process on manufactured parts with surface curvature angles between 0 and 90 degrees.

[0057] To understand how to create an optimal coating design for a coated glass article 100 having a surface curvature (see Figures 1-8), it is important to understand the specific coating process used to form the layers of the optical coating 120, and the level of line-of-sight coating effects that occur during that process. Some coating deposition processes, such as atomic layer deposition, have no line-of-sight behavior at all, such as atomic layer deposition, in which molecules or atoms are deposited one monolayer at a time. However, such processes can be slow (at least as limited by current processing technology) and are generally too expensive for applications involving large substrates or cost-sensitive industries such as the consumer electronics and automotive industries. A more cost-effective process for forming the optical coating 120 is reactive sputtering, which is easily scalable to large areas and can be relatively inexpensive. However, the nature of industrial reactive sputtering processes typically involves deposition with at least some line-of-sight behavior, meaning that the surface of the article directly facing the sputtering target will receive more of the deposited material (resulting in a thicker coating), while the surface of the article that is tilted at an angle relative to the sputtering target (e.g., its curved surface) will generally receive less material, resulting in a thinner coating.

[0058] Thus, in one or more embodiments, the optical coating 120 has been optimized based on a trade-off between hardness, reflectivity, color, and the number of coating layers. Adding any number of layers to the optical coating to achieve an optical goal (e.g., without regard to hardness or other mechanical properties) tends to reduce the hardness of the coating to a level below the range required for scratch-resistant chemically strengthened glass applications for consumer electronics, automotive, and touchscreen applications (e.g., hardness << 12 GPa as measured by a Bosch indenter hardness test at an indentation depth of about 100 nm or greater). In the case of a coated glass article 100 having a curved surface (e.g., at the second portion 115 of the first major surface 112), it may be important to evaluate the relationship between the curvature of the portion of the surface and the amount, or scaling factor, by which the layers of the optical coating 120 are reduced or thinned from their target design thickness. The target design thickness (or thickness at a 100% scaling factor or a 1.0 scaling factor) is typically the thickness applied to "flat" areas of the coated glass article 100 (e.g., at the first portion 113 of the first major surface 112), the portion of the coated glass article 100 closest to directly facing the sputtering target, or the portion of the coated glass article 100 that receives the most material from the sputtering target. Any portion of the coated glass article 100 that curves away from this maximum thickness deposition direction will typically receive less material, resulting in a thinner coating on these curved areas as each layer of the optical coating 120 is formed. For optimal optical coating design of the optical coating 120 of embodiments of the coated glass article 100 (see Figures 1-8), it can be beneficial to understand the design window in terms of target section curvature and how section curvature corresponds to coating thinning during the deposition process. This enables optical design of the optical coating 120 to, for example, optimize reflectivity and color within a target range of section angles and coating thickness variations without sacrificing significant coating hardness, the number of layers in the coating, or other criteria. In other words, without understanding the relevant windows of partial angle and coating thickness scaling factors, it is possible to over-design the coating to include too many layers to achieve a desired set of optical properties, thereby sacrificing hardness and scratch resistance.

[0059] See now Figure 9 , provides a plot of the optical coating thickness scaling factor versus the curvature of a portion of the surface during deposition. Specifically, Figure 9 An experimentally measured correspondence between a partial surface angle (i.e., at the second portion 115 of the first major surface 112) and a coating thickness scaling factor (i.e., for the optical coating 120) for a reactive sputtering process employed on a coated glass article 100 (see Figures 1-8 and corresponding description above) according to an embodiment of the present disclosure is shown. Figure 9 It can be used to establish a target process window to optimize the deposition process of the optical coating used to form the articles of the present disclosure. Figure 9As shown, the coating thickness scaling factor follows the square root of Dependency, where is the partial surface angle. Figure 9 The data shown in were obtained by measuring sputtered thin films using known optical interferometry methods with a sample holder that allows the rotation of a curved section and measurement of the reflectance spectrum at the normal angle at each point along the curvature of the section. Figure 9 As shown, a surface angle of 30 degrees corresponds to a coating thickness scaling factor of about 0.95, 40 degrees corresponds to about 0.85, 50 degrees corresponds to about 0.8, and 60 degrees corresponds to about 0.7. For a coated glass article 100 having a non-planar second portion 115 of 30 degrees, the layer of optical coating 120 over the second portion 115 thereof will be thinner by a scaling factor of 0.85. In other words, the layer thickness of the optical coating 120 over the first portion 113 and over the second portion 115 may vary according to the thickness scaling factor, such as Figure 9 shown.

[0060] See again Figure 9 The disclosed designs of the coated glass articles 100 of the present disclosure can be particularly optimized to have an optical coating 120 characterized by a favorable combination of low reflectivity, controlled color, and controlled color shift with viewing angle (incident light angle) at 100% thickness (1.0 scaling factor) and at thickness scaling factors of 0.7 (70%) or less. To calculate the optical performance for each thickness scaling factor, all layers of the 100% thickness layer design are scaled by the same amount (thickness scaling factor) and the optical results are recalculated using transfer matrix method techniques according to principles understood by those skilled in the art of the present disclosure. The SiO2, SiO2, and SiO2 are measured according to principles understood by those skilled in the art of the present disclosure. x N y and SiN x The optical refractive index dispersion curves of sputter-deposited films of the optical coating 120 (or other materials employed in the layers of the optical coating 120) are obtained and these refractive index dispersion values ​​are input into the optical model.

[0061] According to various embodiments disclosed herein, the thickness of the optical coating 120 on the second portion 115 measured perpendicular to the first major surface 112 at the second portion 115 is 70% or less (i.e., scaled to 0.7 or less) of the thickness of the optical coating 120 on the first portion 113 measured perpendicular to the first major surface 112 at the first portion 113. In additional embodiments, the thickness of the optical coating 120 on the second portion 115 measured perpendicular to the first major surface 112 at the second portion 115 is 65% or less (i.e., scaled to 0.65 or less), 60% or less (i.e., scaled to 0.6 or less), 55% or less (i.e., scaled to 0.55 or less), 50% or less (i.e., scaled to 0.5 or less), 45% or less (i.e., scaled to 0.45 or less), 40% or less (i.e., scaled to 0.4 or less), 35% or less (i.e., scaled to 0.35 or less), or even 30% or less (i.e., scaled to 0.3 or less) of the thickness of the optical coating 120 on the first portion 113 measured perpendicular to the first major surface 112 at the first portion 113.

[0062] According to embodiments described herein, various portions of the coated glass article 100 (e.g., the first portion 113 and the second portion 115) can have similar optical characteristics, such as light reflectance, light transmittance, reflected color, and / or transmitted color, to one another. For example, when each portion is observed at the respective portions 113, 115 in a direction substantially perpendicular to the glass substrate 110 (i.e., θ1 equals approximately 0 degrees and θ2 equals approximately 0 degrees), the optical characteristics at the first portion 113 can be similar to the optical characteristics at the second portion 115. In other embodiments, when each portion is observed at an incident illumination angle within a specified range relative to the normal direction at the respective portions 113, 115 (e.g., θ1 is approximately 0 degrees to approximately 90 degrees and θ2 is approximately 0 degrees to approximately 90 degrees), the optical characteristics at the first portion 113 can be similar to the optical characteristics at the second portion 115. In additional embodiments, the optical characteristics at the first portion 113 may be similar to the optical characteristics at the second portion 115 when each portion is viewed from substantially the same direction (eg, the angle between v1 and v2 is approximately equal to 0 degrees).

[0063] The optical coating 120 includes at least one layer of at least one material. The term "layer" may include a single layer or may include one or more sub-layers. Such sub-layers may be in direct contact with each other. The sub-layers may be formed of the same material or two or more different materials. In one or more alternative embodiments, such sub-layers may have an intermediate layer of a different material disposed therebetween. In one or more embodiments, the layer may include one or more continuous and uninterrupted layers and / or one or more discontinuous and discontinuous layers (i.e., layers of different materials formed adjacent to each other). The layer or sub-layers may be formed by any known method in the art, including discrete deposition processes or continuous deposition processes. In one or more embodiments, the layer may be formed using only a continuous deposition process, or alternatively, using only a discrete deposition process.

[0064] The thickness of the optical coating 120 in the deposition direction can be about 50 nm or greater while still providing an article exhibiting the optical properties described herein. In some examples, the thickness of the optical coating in the deposition direction can be in the range of about 0.05 μm to about 10 μm, about 0.1 μm to about 10 μm, about 0.5 μm to about 5 μm, about 2 μm to about 10 μm, about 2 μm to about 5 μm, about 2 μm to about 4 μm, and all thicknesses of the optical coating 120 between these thickness values. For example, the optical coating 120 can have a thickness of approximately 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, and all thicknesses therebetween.

[0065] As used herein, the term "disposed" includes coating, depositing and / or forming a material onto a surface using any method known in the art. As defined herein, the disposed material may constitute a layer. The phrase "disposed on..." includes situations where the material is formed onto a surface so that the material is in direct contact with the surface, and also includes situations where the material is formed on the surface with one or more intermediate materials located between the disposed material and the surface. As defined herein, one or more intermediate materials may constitute a layer. Additionally, it should be understood that while Figure 2-8 A planar substrate is schematically depicted, but Figure 2-8 It can also be considered as having a non-planar substrate (such as Figure 1A ), and are depicted as flat to simplify the conceptual teaching of the corresponding figures.

[0066] like Figure 2As shown, the optical coating 120 may include an anti-reflective coating 130, which may include a plurality of layers (130A, 130B). In one or more embodiments, the anti-reflective coating 130 may include a period 132 comprising two or more layers. In one or more embodiments, the two or more layers may be characterized by having different refractive indices from one another. In one embodiment, the period 132 includes a first low RI layer 130A and a second high RI layer 130B. The difference in refractive index between the first low RI layer and the second high RI layer may be about 0.01 or greater, about 0.05 or greater, about 0.1 or greater, or even about 0.2 or greater.

[0067] As used herein, the terms "low RI layer" and "high RI layer" refer to the relative values ​​of the refractive index ("RI") of the layers of the optical coating of the transparent article according to the present disclosure (i.e., low RI layer < high RI layer). Thus, the refractive index value of the low RI layer is less than the refractive index value of the high RI layer. Furthermore, as used herein, "low RI layer" and "low refractive index layer" are interchangeable and have the same meaning. Similarly, "high RI layer" and "high refractive index layer" are interchangeable and have the same meaning.

[0068] like Figure 2 As shown, the antireflective coating 130 may include a plurality of periods 132. A single period 132 may include a first low RI layer 130A and a second high RI layer 130B, such that when a plurality of periods 132 are provided, the first low RI layers 130A (designated "L" for illustration purposes) and the second high RI layers 130B (designated "H" for illustration purposes) alternate in the following layer sequence: L / H / L / H or H / L / H / L, such that the first low RI layers 130A and the second high RI layers 130B appear to alternate along the physical thickness of the optical coating 120. Figure 2 In the example of FIG. 1 , the antireflective coating 130 includes three (3) periods 132. In some embodiments, the antireflective coating 130 may include up to twenty-five (25) periods 132 (also referred to herein as "N" periods, where N is an integer). For example, the antireflective coating 130 may include about 2 to about 20 periods 132, about 2 to about 15 periods 132, about 2 to about 12 periods 132, about 2 to about 10 periods 132, about 2 to about 12 periods 132, about 3 to about 8 periods 132, about 3 to about 6 periods 132, or any other period 132 within these ranges. For example, the antireflective coating 130 may include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 periods 132.

[0069] exist Figure 3In the embodiment shown, the anti-reflective coating 130 may include an additional capping layer 131, which may include a material having a lower refractive index than the second high RI layer 130B. Figure 3 As shown, the period 132 may include one or more third layers 130C. The one or more third layers 130C may have a low RI, a high RI, or an intermediate RI. In some embodiments, the one or more third layers 130C may have the same RI as the first low RI layer 130A or the second high RI layer 130B. In other embodiments, the one or more third layers 130C may have an intermediate RI between the RI of the first low RI layer 130A and the RI of the second high RI layer 130B. Alternatively, the one or more third layers 130C may have a greater refractive index than the second high RI layer 130B. The third layer 130C can be arranged in the optical coating 120 in the following exemplary configurations: L third layer / H / L / H / L; H third layer / L / H / L / H; L / H / L / H / L third layer; H / L / H / L / H third layer; L third layer / H / L / H / L / H third layer; H third layer / L / H / L / H / L third layer; L third layer / L / H / L / H; H third layer / H / L / H / L; H / L / H / L / L third layer; L third layer / L / H / L / H / H third layer; H third layer / / H / L / H / L / L third layer; L / M third layer / H / L / M / H; H / M / L / H / M / L; M / L / H / L / M; and other combinations. In these configurations, "L" without any subscript refers to the first low RI layer, and "H" without any subscript refers to the second high RI layer. References to "L third sublayer" refer to the third layer with low RI, "H third sublayer" refers to the third layer with high RI, and "M" refers to the third layer with medium RI, all relative to the first and second layers.

[0070] As used herein, the terms "low RI," "high RI," and "medium RI" refer to the relative value of RI to another RI (e.g., low RI < medium RI < high RI). In one or more embodiments, when used with a first low RI layer or a third layer, the term "low RI" includes a range of about 1.3 to about 1.7 or 1.75. In one or more embodiments, when used with a second high RI layer or a third layer, the term "high RI" includes a range of about 1.7 to about 2.6 (e.g., about 1.85 or greater). In some embodiments, when used with a third layer, the term "medium RI" includes a range of about 1.55 to about 1.8. In some cases, the ranges of low RI, high RI, and medium RI may overlap; however, in most cases, the general relationship of the layers of the anti-reflective coating 130 in terms of RI is: low RI < medium RI < high RI.

[0071] like Figure 4As shown, one or more third layers 130C may be provided as a layer separate from the period 132 and may be disposed between the period 132 or the plurality of periods 132 and the capping layer 131. Figure 5 As shown, one or more third layers may also be provided as a layer separate from the period 132 and may be disposed between the glass substrate 110 and the plurality of periods 132. Figure 6 As shown, one or more third layers 130C may be used in addition to the additional coating 140 in place of the capping layer 131 or in addition to the capping layer 131. Figure 7 and 8 In the configuration depicted in FIG, one or more third layers 130C (not shown) are positioned adjacent to the scratch-resistant layer 150 or the glass substrate 110.

[0072] Materials suitable for the anti-reflective coating 130 include: SiO2, Al2O3, GeO2, SiO, AlO x N y 、AlN、SiN x 、SiO x N y 、Si u Al v O x N y , Ta2O5, Nb2O5, TiO2, ZrO2, TiN, MgO, MgF2, BaF2, CaF2, SnO2, HfO2, Y2O3, MoO3, DyF3, YbF3, YF3, CeF3, polymers, fluoropolymers, plasma-polymerized polymers, siloxane polymers, silsesquioxanes, polyimides, fluorinated polyimides, polyetherimides, polyethersulfones, polyphenylsulfones, polycarbonates, polyethylene terephthalate, polyethylene naphthalate, acrylic polymers, polyurethane polymers, polymethyl methacrylate, other materials listed below as suitable for the scratch resistant layer, and other materials known in the art. Some examples of materials suitable for the first low RI layer include SiO2, Al2O3, GeO2, SiO, AlO x N y 、SiO x N y 、Si u Al v O x N y , MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3 and CeF3. The nitrogen content of the material used for the first low RI layer can be minimized (for example, in materials such as Al2O3 and MgAl2O4). Some examples of materials suitable for the second high RI layer include Si u Alv O x N y , Ta2O5, Nb2O5, AlN, Si3N4, AlO x N y 、SiO x N y 、SiN x 、SiN x :H y , HfO2, TiO2, ZrO2, Y2O3, Al2O3, MoO3 and diamond-like carbon. In an example, the high RI layer can also be a high hardness layer or a scratch-resistant layer, and the high RI materials listed above can also contain high hardness or scratch resistance. The oxygen content of the material used for the second high RI layer and / or the scratch-resistant layer can be minimized, especially in SiN x or AlN x In the material. AlO x N y The material can be considered as oxygen-doped AlN x , i.e. it may have AlN x The AlO crystal structure (e.g., wurtzite) does not necessarily have the AlON crystal structure. x N y The high RI material may contain from about 0 atomic % to about 20 atomic % oxygen or from about 5 atomic % to about 15 atomic % oxygen while including from 30 atomic % to about 50 atomic % nitrogen. u Al v O x N y The high RI material may comprise from about 10 atomic % to about 30 atomic % or from about 15 atomic % to about 25 atomic % silicon, from about 20 atomic % to about 40 atomic % or from about 25 atomic % to about 35 atomic % aluminum, from about 0 atomic % to about 20 atomic % or from about 1 atomic % to about 20 atomic % oxygen, and from about 30 atomic % to about 50 atomic % nitrogen. The foregoing materials may be hydrogenated up to about 30 wt %. Exemplary Si u O x N y The high RI material may comprise 45 atomic % to 50 atomic % silicon, 45 atomic % to 50 atomic % nitrogen, and 3 atomic % to 10 atomic % oxygen. u O x N y High RI materials may contain 45 to 50 atomic % silicon, 35 to 50 atomic % nitrogen, and 3 to 20 atomic % oxygen. When a material with a medium refractive index is required, some embodiments may utilize AlN and / or SiO x N yThe hardness of the second high RI layer and / or the scratch resistant layer can be specifically characterized. In some embodiments, the second high RI layer 130B and / or the scratch resistant layer 150 (see Figure 7 and 8 , and their corresponding descriptions below) can have a maximum hardness of about 8 GPa or greater, about 10 GPa or greater, about 12 GPa or greater, about 15 GPa or greater, about 18 GPa or greater, or about 20 GPa or greater as measured by the Bohr Indenter Hardness Test at an indentation depth of about 100 nm or greater. In some cases, the second high RI layer 130B material can be deposited as a single layer and can be characterized as a scratch resistant layer (e.g., Figure 7 and 8 and further described below), and the thickness of this single layer may be between about 200 nm and 5000 nm to allow for repeatable hardness measurements. Figure 7 and 8 In other embodiments where the scratch-resistant layer 150 (depicted in FIG) is deposited as a single layer, the thickness of this layer can be from about 200 nm to about 5000 nm, from about 200 nm to about 3000 nm, from about 500 nm to about 5000 nm, from about 1000 nm to about 4000 nm, from about 1500 nm to about 4000 nm, from about 1500 nm to about 3000 nm, and all thickness values ​​between these thicknesses.

[0073] In one or more embodiments, at least one layer of the anti-reflective coating 130 may include a specific optical thickness range. As used herein, the term "optical thickness" is determined by the product of the physical thickness of the layer and the intensity attenuation coefficient. In one or more embodiments, at least one layer of the anti-reflective coating 130 may include an optical thickness within the following ranges: about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, about 15 nm to about 500 nm, or about 15 nm to about 5000 nm. In some embodiments, all layers of the anti-reflective coating 130 may each have an optical thickness within the following ranges: about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, about 15 nm to about 500 nm, or about 15 nm to about 5000 nm. In some cases, the optical thickness of at least one layer of the anti-reflective coating 130 is about 50 nm or greater. In some cases, each first low RI layer has an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, about 15 nm to about 500 nm, or about 15 nm to about 5000 nm. In other cases, each second high RI layer has an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, about 15 nm to about 500 nm, or about 15 nm to about 5000 nm. In still other cases, each third layer has an optical thickness in the range of about 2 nm to about 200 nm, about 10 nm to about 100 nm, about 15 nm to about 100 nm, about 15 nm to about 500 nm, or about 15 nm to about 5000 nm.

[0074] In some embodiments, the topmost air-side layer may comprise a high RI layer 130B that also exhibits high hardness (see Figure 2 In some embodiments, an additional coating 140 may be placed on top of this topmost air-side high RI layer (see Figure 6 and their corresponding descriptions below) (e.g., the additional coating may include a low-friction coating, an oleophobic coating, or an easy-to-clean coating). When a low-RI layer of very low thickness (e.g., about 10 nm or less, about 5 nm or less, or about 2 nm or less) is added to the topmost air-side layer comprising a high-RI layer, the addition has minimal effect on optical performance. The low-RI layer of very low thickness may include SiO2, an oleophobic layer, or a low-friction layer, or a combination of SiO2 and an oleophobic material. An exemplary low-friction layer may include diamond-like carbon, and such a material (or one or more layers of an optical coating) may exhibit a coefficient of friction of less than 0.4, less than 0.3, less than 0.2, or even less than 0.1.

[0075] In one or more embodiments, the anti-reflective coating 130 may have a physical thickness of about 800 nm or less. The anti-reflective coating 130 may have a physical thickness in the following ranges: about 10 nm to about 800 nm, about 50 nm to about 800 nm, about 100 nm to about 800 nm, about 150 nm to about 800 nm, about 200 nm to about 800 nm, about 300 nm to about 800 nm, about 400 nm to about 800 nm, about 10 nm to about 750 nm, about 10 nm to about 700 nm, about 10 nm to about 650 nm, about 10 nm to about 600 nm, about 10 nm to about 550 nm, about 10 nm to about 500 nm, about 10 nm to about 450 nm, about 10 nm to about 400 nm, about 10 nm to about 350 nm, about 10 nm to about 300 nm, about 50 nm to about 300 nm, and all ranges and sub-ranges therebetween. In some embodiments, the anti-reflective coating 130 can have a physical thickness within the range of about 250 nm to about 1000 nm, about 500 nm to about 1000 nm, and all ranges and sub-ranges therebetween. For example, the anti-reflective coating 130 can have a physical thickness of about 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, and all thicknesses between these thickness values.

[0076] In one or more embodiments, the anti-reflective coating 130 may be disposed over the scratch-resistant layer 150. It has been found that limiting the thickness of the anti-reflective coating 130 over the scratch-resistant layer 150 can increase hardness. In one or more embodiments, the physical thickness of the anti-reflective coating 130 disposed over the scratch-resistant layer 150 may be approximately 1000 nm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, or even 400 nm or less.

[0077] In one or more embodiments, the combined physical thickness of the one or more second high RI layers may be characterized. For example, in some embodiments, the combined thickness of the one or more second high RI layers may be about 100 nm or greater, about 150 nm or greater, about 200 nm or greater, about 250 nm or greater, about 300 nm or greater, about 350 nm or greater, about 400 nm or greater, about 450 nm or greater, about 500 nm or greater, about 550 nm or greater, about 600 nm or greater, about 650 nm or greater, about 700 nm or greater, about 750 nm or greater, about 800 nm or greater, about 850 nm or greater, about 900 nm or greater, about 950 nm or greater, or even about 1000 nm or greater. The combined thickness is the calculated combination of the thicknesses of the individual high RI layers in the antireflective coating 130, even if one or more low RI layers or one or more other layers are present in between. In some embodiments, the combined physical thickness of the one or more second high RI layers (which may also include a high hardness material (e.g., a nitride or oxynitride material)) may be greater than 30% of the total physical thickness of the antireflective coating. For example, the combined physical thickness of the one or more second high RI layers may be about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 75% or more, or even about 80% or more of the total physical thickness of the antireflective coating 130 or the total physical thickness of the optical coating 120. Additionally or alternatively, the amount of high refractive index material (which may also be a high hardness material) included in the optical coating may be characterized as a percentage of the physical thickness of the uppermost 500 nm of the article or optical coating 120 (i.e., the user side or the side of the optical coating opposite the substrate). Expressed as a percentage of the uppermost 500 nm of the article or optical coating, the combined physical thickness of the one or more second high RI layers (or the thickness of the high refractive index material) may be about 50% or more, about 60% or more, about 70% or more, about 80% or more, or even about 90% or more. In some embodiments, the proportion of hard and high refractive index materials in the anti-reflective coating can also be increased simultaneously, thereby also exhibiting low reflectivity, low color, and high abrasion resistance, as further described elsewhere herein. In one or more embodiments, the second high RI layer can include a material with a refractive index greater than about 1.85, while the first low RI layer can include a material with a refractive index less than about 1.75. In some embodiments, the second high RI layer can include a nitride or oxynitride material. In some cases, the combined thickness of all first low RI layers in the optical coating (or in a layer disposed above the thickest second high RI layer of the optical coating) can be about 200 nm or less (e.g., about 150 nm or less, about 100 nm or less, about 75 nm or less, or about 50 nm or less).

[0078] like Figure 6As shown, the coated glass article 100 may include one or more additional coatings 140 disposed over the antireflective coating. In one or more embodiments, the additional coating may include an easy-to-clean coating. Examples of suitable easy-to-clean coatings are described in U.S. Patent Application No. 13 / 690,904, filed on November 30, 2012, entitled "Process for Making of Glass Articles with Optical and Easy-to-Clean Coatings," which was published as U.S. Patent Application Publication No. 2014 / 0113083 on April 24, 2014, the respective portions of which are incorporated herein by reference in their entirety. The easy-to-clean coating may have a thickness ranging from about 5 nm to about 50 nm and may include known materials, such as fluorinated silanes. The easy-to-clean coating may alternatively or additionally include a low-friction coating or surface treatment. Exemplary low-friction coating materials may include diamond-like carbon, silanes (e.g., fluorosilanes), phosphonates, olefins, and alkynes. In some embodiments, the thickness of the easy-to-clean coating may have a thickness in the range of about 1 nm to about 40 nm, about 1 nm to about 30 nm, about 1 nm to about 25 nm, about 1 nm to about 20 nm, about 1 nm to about 15 nm, about 1 nm to about 10 nm, about 5 nm to about 50 nm, about 10 nm to about 50 nm, about 15 nm to about 50 nm, about 7 nm to about 20 nm, about 7 nm to about 15 nm, about 7 nm to about 12 nm, or about 7 nm to about 10 nm, and all ranges and sub-ranges therebetween.

[0079] The additional coating 140 may include one or more scratch-resistant layers. In some embodiments, the additional coating 140 includes a combination of an easy-to-clean material and a scratch-resistant material. In one example, the combination includes an easy-to-clean material and diamond-like carbon. The thickness of such an additional coating 140 may range from about 5 nm to about 20 nm. The components of the additional coating 140 may be provided as separate layers. For example, the diamond-like carbon may be provided as a first layer, and the easy-to-clean material may be provided as a second layer on the first layer of diamond-like carbon. The thicknesses of the first and second layers may be within the ranges provided above for the additional coating. For example, the thickness of the first layer of diamond-like carbon may be from about 1 nm to about 20 nm or from about 4 nm to about 15 nm (or, more specifically, about 10 nm), and the thickness of the second layer of easy-to-clean material may be from about 1 nm to about 10 nm (or, more specifically, about 6 nm). The diamond-like coating may include tetrahedral amorphous carbon (Ta—C), Ta—C:H, and / or aCH.

[0080] As mentioned herein, the optical coating 120 may include a scratch-resistant layer 150, which may be disposed between the anti-reflective coating 130 and the glass substrate 110. In some embodiments, the scratch-resistant layer 150 is disposed between layers of the anti-reflective coating 130 (e.g., Figure 7 and 8 The two portions of the anti-reflective coating 130 (i.e., the first portion disposed between the scratch-resistant layer 150 and the glass substrate 110, and the second portion disposed on the scratch-resistant layer) may have different thicknesses than one another, or may have substantially the same thickness as one another. The layers of the two portions of the anti-reflective coating 130 may be identical to one another in composition, order, thickness, and / or arrangement, or may be different from one another. Furthermore, the layers of the two portions of the anti-reflective coating 130 may include the same number of periods 132 (N), or the number of periods 132 in each of these portions may be different from one another (see Figure 2-6 132 as shown and previously described). In addition, one or more optional layers 130C (not shown) can be disposed in either or both of the two portions (e.g., directly on the glass substrate 110, on top of the portion of the first anti-reflective coating 130 in contact with the scratch-resistant layer 150, on the bottom of the portion of the second anti-reflective coating 130 in contact with the scratch-resistant layer 150, and / or on the bottom of the second anti-reflective coating in contact with the glass substrate 110).

[0081] Exemplary materials used in the scratch resistant layer 150 (or the scratch resistant layer used as the additional coating 140) may include inorganic carbides, nitrides, oxides, diamond-like materials, or combinations of these materials. Examples of suitable materials for the scratch resistant layer 150 include metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal oxycarbides, and / or combinations thereof. Exemplary metals include B, Al, Si, Ti, V, Cr, Y, Zr, Nb, Mo, Sn, Hf, Ta, and W. Specific examples of materials that can be used for the scratch resistant layer 150 or coating may include Al2O3, AlN, AlO x N y 、Si3N4、SiO x N y 、Si u Al v O x N y 、SiN x , diamond, diamond-like carbon, Si x C y 、Si x O y C z 、ZrO2、TiO x N yand combinations thereof. The scratch-resistant layer 150 may also comprise a nanocomposite material or a material with a controlled microstructure to enhance hardness, toughness, or wear / abrasion resistance. For example, the scratch-resistant layer 150 may comprise nanocrystallites having a size range of about 5 nm to about 30 nm. In embodiments, the scratch-resistant layer 150 may comprise transformation-toughened zirconia, partially stabilized zirconia, or zirconia-toughened alumina. In embodiments, the scratch-resistant layer 150 exhibits a fracture toughness value greater than about 1 MPa√m and simultaneously exhibits a hardness value greater than about 12 GPa.

[0082] The scratch resistant layer 150 may include a single layer (e.g. Figure 7 and 8 ), or multiple sub-layers or a single layer exhibiting a refractive index gradient. When multiple layers are used, such layers form a scratch-resistant coating. For example, the scratch-resistant layer 150 may include Si u Al v O x N y A composition gradient is formed in which the concentration of any one or more of Si, Al, O, and N is varied to increase or decrease the refractive index. A refractive index gradient can also be formed using porosity. Such a gradient is more fully described in U.S. Patent Application No. 14 / 262,224, entitled "Scratch-Resistant Articles with a Gradient Layer," filed on April 28, 2014, which now issued as U.S. Patent No. 9,703,011 on July 11, 2017, the highlights of each of which are hereby incorporated by reference in their entirety.

[0083] According to some embodiments, the thickness of the scratch resistant layer 150 can be from about 200 nm to about 5000 nm. In some implementations, the thickness of the scratch resistant layer 150 is from about 200 nm to about 5000 nm, from about 200 nm to about 3000 nm, from about 500 nm to about 5000 nm, from about 500 nm to about 3000 nm, from about 500 nm to about 2500 nm, from about 1000 nm to about 4000 nm, from about 1500 nm to about 4000 nm, from about 1500 nm to about 3000 nm, and all thickness values ​​between these thicknesses. For example, the scratch resistant layer 150 can have a thickness of 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, 1600 nm, 1700 nm, 1800 nm, 1900 nm, 2000 nm, 2100 nm, 2200 nm, 2300 nm, 2400 nm, 2500 nm, 2600 nm, 2700 nm, 2800 nm, 2900 nm, 3000 nm, 3500 nm, 4000 nm, 4500 nm, 5000 nm, and all thickness subranges and thickness values ​​therebetween.

[0084] exist Figure 8 In one embodiment depicted in FIG, the optical coating 120 may include a scratch-resistant layer 150 integrated as a high RI layer, and one or more low RI layers 130A and high RI layers 130B may be positioned above the scratch-resistant layer 150, with an optional capping layer 131 positioned above the low RI layer 130A and high RI layer 130B, wherein the capping layer 131 comprises a low RI material. The scratch-resistant layer 150 may alternatively be defined as the thickest hard layer or the thickest high RI layer in the entire optical coating 120 or the entire coated glass article 100. Without being bound by theory, it is believed that when a relatively small amount of material is deposited above the scratch-resistant layer 150, the coated glass article 100 may exhibit increased hardness at the indentation depth. However, the inclusion of low RI and high RI layers above the scratch-resistant layer 150 may enhance the optical properties of the coated glass article 100. In some embodiments, a relatively small number of layers (e.g., only 1, 2, 3, 4, or 5 layers) may be positioned over the scratch-resistant layer 150, and each of these layers may be relatively thin (e.g., less than 100 nm, less than 75 nm, less than 50 nm, or even less than 25 nm). In other embodiments, a greater number of layers (e.g., 3 to 15 layers) may be positioned over the scratch-resistant layer 150, and each of these layers may also be relatively thin (e.g., less than 200 nm, less than 175 nm, less than 150 nm, less than 125 nm, less than 100 nm, less than 75 nm, less than 50 nm, and even less than 25 nm). Figure 8 In one implementation of the embodiment depicted in FIG, the anti-reflective coating 130 may include: periods 132 including four periods 132 above the scratch-resistant layer 150 and four periods 132 below the scratch-resistant layer (i.e., N=8); a layer 130C (not shown) disposed adjacent to the scratch-resistant layer 150 or the glass substrate 110; and a capping layer 131 (e.g., Figure 8 shown). Figure 8 In another implementation of the embodiment depicted in FIG, the antireflective coating 130 may include: periods 132 including five periods 132 above the scratch-resistant layer 150 and five periods 132 below the scratch-resistant layer (i.e., N=8); a layer 130C (not shown) disposed adjacent to the scratch-resistant layer 150 or the glass substrate 110; and a capping layer 131 (e.g., Figure 8 shown).

[0085] In embodiments, the total thickness (i.e., combined thickness) of the layers deposited over the scratch resistant layer 150 (i.e., on the air side of the scratch resistant layer 150) may be less than or equal to about 1000 nm, less than or equal to about 500 nm, less than or equal to about 450 nm, less than or equal to about 400 nm, less than or equal to about 350 nm, less than or equal to about 300 nm, less than or equal to about 250 nm, less than or equal to about 225 nm, less than or equal to about 200 nm, less than or equal to about 175 nm, less than or equal to about 150 nm, less than or equal to about 125 nm, less than or equal to about 100 nm, less than or equal to about 90 nm, less than or equal to about 80 nm, less than or equal to about 70 nm, less than or equal to about 60 nm, or even less than or equal to about 50 nm.

[0086] In the embodiments (e.g., Figure 7 and 8 ), the total thickness of the one or more low RI layers positioned above the scratch resistant layer 150 (i.e., on the air side of the scratch resistant layer 150) (the sum of the thicknesses of all low RI layers 130A, even if they are not in contact) can be less than or equal to about 500 nm, less than or equal to about 450 nm, less than or equal to about 400 nm, less than or equal to about 350 nm, less than or equal to about 300 nm, less than or equal to about 250 nm, less than or equal to about 200 nm, or less than or equal to about 250 nm. less than or equal to about 25 nm, less than or equal to about 200 nm, less than or equal to about 175 nm, less than or equal to about 150 nm, less than or equal to about 125 nm, less than or equal to about 100 nm, less than or equal to about 90 nm, less than or equal to about 80 nm, less than or equal to about 70 nm, less than or equal to about 60 nm, less than or equal to about 50 nm, less than or equal to about 40 nm, less than or equal to about 30 nm, less than or equal to about 20 nm, or even less than or equal to about 10 nm.

[0087] In embodiments, when the optical coating 120 includes one or more layers exhibiting a refractive index gradient, i.e., a gradient layer, the configuration of the optical coating may be substrate / gradient layer / scratch-resistant layer / anti-reflective layer. In other embodiments, the configuration of the optical coating 120 may be substrate / anti-reflective layer / scratch-resistant layer / gradient layer. In yet other embodiments, the configuration of the optical coating may be substrate / first gradient layer / scratch-resistant layer / second gradient layer.

[0088] The optical coating 120 and / or coated glass article 100 can be described in terms of hardness as measured by the Bohr indenter hardness test. As used herein, the "Bohr indenter hardness test" involves measuring the hardness of a material on its surface by pressing a diamond Bohr indenter into the surface. The Bohr indenter hardness test includes pressing a diamond Bohr indenter into the antireflective surface 122 of the coated glass article 100 (see Figures 1-8) or the surface of any one or more layers of the optical coating 120 to form an indentation having a depth in the range of about 50 nm to about 1000 nm (or the entire thickness of the optical coating 120 or a layer thereof, whichever is less) and measuring the maximum hardness of the indentation along the entire indentation depth range or a portion of the indentation depth (e.g., in the range of about 100 nm to about 600 nm, such as at an indentation depth of 100 nm or greater, etc.), the test being generally conducted using the method described in Oliver, WC; Pharr, GM, "An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation." experiments)," J. Mater. Res., Vol. 7, No. 6, 1992, 1564-1583; and Oliver, WC; Pharr, GM, "Measurement of Hardness and Elastic Modulus by Instrument Indentation: Advances in Understanding and Refinements to Methodology", J. Mater. Res., Vol. 19, No. 1, 2004, 3-20, the highlights of which are incorporated herein by reference in their entirety. As used herein, "hardness" refers to the maximum hardness, not the average hardness.

[0089] As used herein, "Bosch indenter hardness test" and "Bosch hardness test" are used interchangeably to refer to a test that measures the hardness of a material on its surface by pressing a diamond Bosch indenter into the surface. The Bohr indenter hardness test comprises pressing a diamond Bohr indenter into the outermost surface (e.g., exposed surface) of a single optical coating or outer optical coating of a transparent article of the present disclosure to form an indentation with a diamond Bohr indenter having an indentation depth in the range of about 50 nm to about 1000 nm (or the entire thickness of the outer optical coating or the inner optical coating, whichever is less), and measuring the maximum hardness from the indentation along the entire indentation depth range or a portion of the indentation depth (e.g., in the range of about 100 nm to about 600 nm), the test generally being performed using the methods described in: Oliver, W.C.; Pharr, G.M. An Improved Technique for Determining Hardness and Elastic Modulus Using Load and Displacement Sensing Indentation Experiments. Journal of Materials Research, Vol. 7, No. 6, 1992, 1564-1583; and Oliver, W.C.; Pharr, G.M. Measurement of Hardness and Elastic Modulus by Instrumented Indentation: Advances in Understanding and Improvements in Methods. Journal of Materials Research, Vol. 19, No. 1, 2004, 3-20. As used herein, "hardness" and "maximum hardness" each refer interchangeably to the maximum hardness measured along a range of indentation depths, rather than the average hardness.

[0090] Typically, when performing nanoindentation measurement methods on a coating with a higher hardness than the underlying substrate (e.g., by using a Bosch indenter), the measured hardness may appear to initially increase due to the development of a plastic zone at shallow indentation depths, and then increase and reach a maximum or plateau at deeper indentation depths. Thereafter, the hardness begins to decrease at deeper indentation depths due to the influence of the underlying substrate. The same effect is seen when utilizing a substrate with a higher hardness than the coating; however, the hardness increases at deeper indentation depths due to the influence of the underlying substrate.

[0091] The indentation depth range and the hardness values ​​within certain indentation depth ranges can be selected to identify specific hardness responses of the optical film structures and their layers described herein, independent of the influence of the underlying substrate. When the hardness of an optical film structure (when placed on a substrate) is measured with a Bosch indenter, the permanent deformation region (plastic zone) of the material is related to the hardness of the material. During indentation, the elastic stress field extends far beyond this permanent deformation region. As the indentation depth increases, the apparent hardness and modulus are affected by the interaction of the stress field with the underlying substrate. The effect of the substrate on hardness occurs at deeper indentation depths (i.e., typically at a depth greater than about 10% of the thickness of the optical film structure or layer). In addition, another complication is that the hardness response requires a minimum load to produce complete plasticity during the indentation process. Before the minimum load, the hardness generally tends to increase.

[0092] At small indentation depths (also characterized by low loads) (e.g., up to approximately 50 nm), the material's apparent hardness appears to increase dramatically relative to the indentation depth. This small indentation depth range does not represent a true indicator of hardness, but rather reflects the development of the aforementioned plastic zone, which is related to the finite radius of curvature of the indenter. At moderate indentation depths, the apparent hardness approaches a maximum level. At deeper indentation depths, the influence of the substrate becomes more pronounced as the indentation depth increases. Once the indentation depth exceeds approximately 30% of the thickness of the optical coating 120, or layer thickness, the hardness begins to decrease dramatically.

[0093] In some embodiments, the coated glass article 100 (e.g., as depicted in Figures 1-8) can exhibit a hardness of about 10 GPa or greater, about 15 GPa or greater, about 20 GPa or greater, about 25 GPa or greater, or about 30 GPa or greater (e.g., about 10 GPa or greater, about 11 GPa or greater, about 12 GPa or greater, about 13 GPa or greater, about 14 GPa or greater, about 15 GPa or greater, about 16 GPa or greater, about 17 GPa or greater, about 18 GPa or greater, about 19 GPa or greater, about 20 GPa or greater, about 21 GPa or greater, about 22 GPa or greater, about 23 GPa or greater, about 24 GPa or greater, about 25 GPa or greater, about 26 GPa or greater, about 27 GPa or greater, about 28 GPa or greater, about 29 GPa or greater, about 30 GPa or greater) when measured at the anti-reflective surface 122. The hardness of the coated glass article 100 can even be as high as about 20 GPa or 30 GPa. The optical coating 120 and / or the coated glass article 100 can exhibit such measured hardness values ​​along an indentation depth of about 50 nm or greater or about 100 nm or greater (e.g., about 50 nm to about 300 nm, about 50 nm to about 400 nm, about 50 nm to about 500 nm, about 50 nm to about 600 nm, about 100 nm to about 300 nm, about 100 nm to about 400 nm, about 100 nm to about 500 nm, about 100 nm to about 600 nm, about 200 nm to about 300 nm, about 200 nm to about 400 nm, about 200 nm to about 500 nm, or about 200 nm to about 600 nm). In one or more embodiments, the coated glass article 100 exhibits a hardness greater than the hardness of the glass substrate 110 (which can be measured on the surface opposite the anti-reflective surface). Unless otherwise stated, hardness may be measured perpendicular to the thickest portion of the optical coating 120 .

[0094] According to embodiments, the hardness can be measured at different portions of the coated glass article 100. For example, at the anti-reflective surface 122 at the first portion 113 and the second portion 115, the coated article can exhibit a hardness of at least 12 GPa or greater at an indentation depth of at least about 600 nm. For example, the hardness at the first portion 113 and the second portion 115 can be about 15 GPa or greater, about 17.5 GPa or greater, or about 20 GPa or greater (e.g., about 15 GPa or greater, about 16 GPa or greater, about 17 GPa or greater, about 18 GPa, about 19 GPa, or about 20 GPa or greater).

[0095] Depending on the embodiment, the coated articles described herein can have desirable optical properties (e.g., low reflectivity and neutral color) at different portions of the coated glass article 100, such as the first portion 113 and the second portion 115. For example, when each portion is viewed at an incident illumination angle that is approximately perpendicular to the respective portion, the reflectivity of light at the first portion 113 and the second portion 115 can be relatively low (while the transmittance can be relatively high). In another embodiment, when each portion is viewed at an incident illumination angle that is approximately perpendicular to the respective portion, the color difference between the two portions can be imperceptible to the naked eye. In another embodiment, when the portions are viewed at incident illumination angles that are in the same direction, the color can be imperceptible to the naked eye, and the reflectivity at each portion can be relatively low (i.e., the incident illumination angle relative to the surface of each portion is different because the portions are angled relative to each other, but illuminated in the same direction). Optical properties may include average light transmittance, average light reflectance, photopic reflectance, maximum photopic reflectance, photopic transmittance, reflected color (ie, expressed in L*a*b* color coordinates), and transmitted color (ie, expressed in L*a*b* color coordinates).

[0096] As used herein, the term "transmittance" refers to the percentage of incident light power transmitted through a material (e.g., an article, substrate, or optical film, or portion thereof) within a given wavelength range. The term "reflectance" is similarly defined as the percentage of incident light power reflected from a material (e.g., an article, substrate, or optical film, or portion thereof) within a given wavelength range. Reflectance can be measured as single-sided reflectance (also referred to herein as "first-surface reflectance") when measured only at the antireflective surface 122 (e.g., when reflections from the uncoated back surface of the article (e.g., 114 in FIG. 1 ) are removed, such as by using an index-matching oil coupled to an absorber on the back surface or other known methods). In one or more embodiments, the spectral resolution of the transmittance and reflectance characterizations is less than 5 nm or 0.02 eV. Color may be more pronounced in reflection. The angular color shift in reflection with viewing angle is due to the shift in the spectral reflectance oscillation with changes in the incident illumination angle. The angular color shift in transmission with viewing angle is also due to the same shift in the spectral transmittance oscillation with changes in the incident illumination angle. Observed color variations with incident illumination angle and angular color shifts are often distracting or objectionable to device users, particularly under lighting with sharp spectral features (e.g., fluorescent lighting and some LED lighting). Angular color shifts in transmission may also affect color shifts in reflection, and vice versa. Angular color shift factors in transmission and / or reflection may also include angular color shifts due to viewing angle, or angular color shifts from a certain white point that may be caused by material absorption (which is somewhat angle-independent) defined by a particular illuminant or test system.

[0097] The coated glass article 100 can also be characterized by its photopic transmittance and reflectance at various portions thereof. As used herein, photopic reflectance simulates the response of the human eye by weighting the reflectance with the wavelength spectrum according to the sensitivity of the human eye. According to known conventions, such as the CIE color space convention, photopic reflectance can also be defined as the brightness or tristimulus Y value of the reflected light. The average photopic reflectance is defined in the following equation (1) as the spectral reflectance R(λ) multiplied by the illuminant spectrum I(λ) and the CIE color matching function related to the spectral response of the eye:

[0098]

[0099] Furthermore, "average reflectivity" can be determined in the visible spectrum or other wavelength ranges (e.g., in the infrared spectrum from 840 nm to 950 nm, etc.) according to measurement principles understood by those skilled in the art of the present disclosure. Unless otherwise specified, all reflectivity values ​​reported or otherwise referenced in this disclosure are related to tests conducted on both major surfaces of the substrate and one or more optical film structures of the transparent article of the present disclosure, such as "dual-surface" average photopic reflectivity. Where "one surface" or "first surface" reflectivity is specified, the reflectivity of the rear surface of the article is eliminated by optical bonding with a light absorber, thereby allowing the reflectivity of only the first surface to be measured.

[0100] The usability of a transparent article in an electronic device (e.g., as a protective cover) may be related to the total amount of reflectivity in the article. Photopic reflectivity is particularly important for display devices that use visible light. Reducing the reflectivity of a cover transparent article over a lens and / or display associated with the device can reduce multiple bounce reflections in the device that can produce "ghost images." Therefore, reflectivity has an important relationship with the image quality associated with the device, particularly its display and any other optical components thereof (e.g., a camera lens). Low reflectivity displays can also improve display readability, reduce eye fatigue, and speed up user response time (e.g., in automotive displays, where display readability may also be related to driver safety). Low reflectivity displays can also allow for reduced display energy consumption and extended device battery life because the display brightness of a low reflectivity display can be reduced compared to a standard display while still maintaining a target level of display readability in bright ambient environments.

[0101] The average photopic transmittance is defined in equation (2) as the spectral transmittance T(λ) multiplied by the illuminant spectrum I(λ) and the CIE color matching function related to the eye's spectral response:

[0102]

[0103] It will also be understood that photopic transmittance and / or reflectance may be reported as the maximum photopic transmittance and / or reflectance within a given spectral range (eg, 425 nm to 950 nm).

[0104] According to an embodiment, Figures 1A-1BThe coated glass article 100 depicted in FIG can exhibit an average two-sided or two-surface (i.e., through both major surfaces 112, 114 of the glass substrate 110) photopic transmittance, or average visible light transmittance, of about 85% or greater, about 88% or greater, about 90% or greater, about 91% or greater, about 92% or greater, about 93% or greater, or even about 94% or greater over the 400 to 700 nm wavelength region at normal incidence, 0 to 10 degrees, 0 to 20 degrees, 0 to 30 degrees, 0 to 40 degrees, 0 to 50 degrees, or even 0 to 60 degrees. In some embodiments, the coated glass article 100 may exhibit an average two-sided transmittance of about 85% or greater, about 88% or greater, about 90% or greater, about 91% or greater, about 92% or greater, about 93% or greater, or even about 94% or greater in the infrared spectrum (e.g., at 940 nm) at normal incidence, 0 to 10 degrees, 0 to 20 degrees, 0 to 30 degrees, 0 to 40 degrees, 0 to 50 degrees, or even 0 to 60 degrees. In some embodiments, the coated glass article 100 may exhibit an average two-sided transmittance in the near infrared spectrum (e.g., average transmittance from 1000 to 1700 nm) of about 80% or greater, about 85% or greater, about 88% or greater, about 90% or greater, about 91% or greater, about 92% or greater, or even about 93% or greater at normal incidence, 0 to 10 degrees, 0 to 20 degrees, 0 to 30 degrees, 0 to 40 degrees, 0 to 50 degrees, or even 0 to 60 degrees.

[0105] According to embodiments described herein, reflectivity may be relatively low in wavelength bands extending to the infrared (IR) spectrum. Generally speaking, visible light and IR light form an interface at about 700nm. Surprisingly, it has been found that extending low reflectivity to the IR band is beneficial for coatings with reduced thickness due to, for example, line-of-sight deposition. In other words, a coating can be designed for thick areas with low IR reflectivity (e.g., above the first portion 113), and conversely, a coating with reduced thickness (e.g., above the second portion 115) will maintain low reflectivity within visible light wavelengths. Without being bound by theory, it is believed that as the coating thickness decreases, the bandwidth range of the low reflectivity band in the coating will decrease. In some embodiments, the band edge of the low reflectivity bandwidth can be scaled roughly linearly with the coating thickness. For example, a coating having a reflectivity of 3% or less at most 1500 nm in a thick portion can have a reflectivity of 3% or less at most about 750 nm in a portion that is half the thickness of its thick portion, or a coating having a reflectivity of 3% or less at most 1500 nm in a thick portion can have a reflectivity of 3% or less at most about 1000 nm in a portion that is two-thirds the thickness of its thick portion. Thus, it was discovered that improvements in coating systems on curved surfaces can be observed when the coating has low IR reflectivity in its thick portion.

[0106] According to one or more embodiments, the coated glass article 100 can exhibit a single-sided light reflectance of about 3% or less at all wavelengths from 410 nm to at least 1050 nm measured at an incident angle of 5 degrees at the anti-reflective surface 122 at the first portion 113 of the glass substrate 110 . In additional embodiments, the coated glass article 100 can exhibit a single-sided light reflectance of about 3% or less at all wavelengths from 410 nm to at least 1100 nm, at least 1150 nm, at least 1200 nm, at least 1250 nm, at least 1300 nm, at least 1350 nm, at least 1400 nm, at least 1450 nm, at least 1500 nm, at least 1550 nm, at least 1600 nm, at least 1650 nm, at least 1700 nm, at least 1750 nm, at least 1800 nm, at least 1850 nm, at least 1900 nm, at least 1950 nm, or even at least 2000 nm, measured at an angle of incidence of 5 degrees at the anti-reflective surface 122 at the first portion 113 of the glass substrate 110. In some embodiments, the first portion 113 resembles the thickest portion of the optical coating 120, as described herein.

[0107] In additional embodiments, the anti-reflective surface 122 at the first portion 113 of the glass substrate 110 has a wavelength of 410 nm to at least 1050 nm, at least 1100 nm, at least 1150 nm, at least 1200 nm, at least 1250 nm, at least 1300 nm, at least 1350 nm, at least 1400 nm, at least 1450 nm, at least 1500 nm, at least 1550 nm, at least 1600 nm, at least 1650 nm, at least 1700 nm, at least 1750 nm, at least 1800 nm, at least 1850 nm, at least 1860 nm, at least 1870 nm, at least 1880 nm, at least 1890 nm, at least 1900 nm, at least 2000 nm, at least 2100 nm, at least 2200 nm, at least 2250 nm, at least 2300 nm, at least 2350 nm, at least 2400 nm, at least 2450 nm, at least 2500 nm, at least 25 The coated glass article 100 can exhibit a single-sided light reflectance of about 2.8% or less, about 2.6% or less, about 2.4% or less, about 2.2% or less, about 2% or less, about 1.8% or less, about 1.6% or less, about 1.4% or less, about 1.2% or less, or even about 1% or less at all wavelengths of at least 50 nm, at least 1800 nm, at least 1850 nm, at least 1900 nm, at least 1950 nm, and even at least 2000 nm, for all combinations of the disclosed reflectance percentages, wavelength ranges, and angles of incidence.

[0108] According to one or more embodiments, the coated glass article 100 can exhibit an average single-sided light reflectance of about 3% or less at a wavelength of 410 nm to at least 1050 nm measured at an incident angle of 5 degrees at the anti-reflective surface 122 at the first portion 113 of the glass substrate 110 . In additional embodiments, the coated glass article 100 can exhibit an average single-sided light reflectance of about 3% or less at all wavelengths from 410 nm to at least 1100 nm, at least 1150 nm, at least 1200 nm, at least 1250 nm, at least 1300 nm, at least 1350 nm, at least 1400 nm, at least 1450 nm, at least 1500 nm, at least 1550 nm, at least 1600 nm, at least 1650 nm, at least 1700 nm, at least 1750 nm, at least 1800 nm, at least 1850 nm, at least 1900 nm, at least 1950 nm, or even at least 2000 nm, measured at an angle of incidence of 5 degrees at the anti-reflective surface 122 at the first portion 113 of the glass substrate 110. In some embodiments, the first portion 113 resembles the thickest portion of the optical coating 120, as described herein.

[0109] In additional embodiments, the anti-reflective surface 122 at the first portion 113 of the glass substrate 110 has a wavelength of 410 nm to at least 1050 nm, at least 1100 nm, at least 1150 nm, at least 1200 nm, at least 1250 nm, at least 1300 nm, at least 1350 nm, at least 1400 nm, at least 1450 nm, at least 1500 nm, at least 1550 nm, at least 1600 nm, at least 1650 nm, at least 1700 nm, at least 1750 nm, at least 1800 nm, at least 1850 nm, at least 1860 nm, at least 1870 nm, at least 1880 nm, at least 1890 nm, at least 1900 nm, at least 2000 nm, at least 2100 nm, at least 2200 nm, at least 2250 nm, at least 2300 nm, at least 2350 nm, at least 2400 nm, at least 2450 nm, at least 2500 nm, at least 25 The coated glass article 100 can exhibit an average single-sided light reflectance of about 2.8% or less, about 2.6% or less, about 2.4% or less, about 2.2% or less, about 2% or less, about 1.8% or less, about 1.6% or less, about 1.4% or less, about 1.2% or less, or even about 1% or less at a wavelength of at least 50 nm, at least 1800 nm, at least 1850 nm, at least 1900 nm, at least 1950 nm, or even at least 2000 nm, for all combinations of the disclosed reflectance percentages, wavelength ranges, and angles of incidence.

[0110] In additional embodiments, the coated glass article 100 may exhibit a single-sided photopic average light reflectance of about 12% or more, about 15% or more, about 20% or more, about 25% or more, about 30% or more, or even 50% or more at a wavelength of about 400 nm to about 700 nm. In further embodiments, the coated glass article 100 may exhibit a single-sided maximum reflectance of about 12% or more, about 15% or more, about 20% or more, about 25% or more, about 30% or more, or even 50% or more at a wavelength of about 400 nm to about 700 nm.

[0111] According to embodiments disclosed herein, the reflected color of the coated glass article 100 at the first portion 113 and the second portion 115 can be relatively colorless. As used herein, color refers to a* and b* in reflection and / or transmission under the CIE L*, a*, b* colorimetric system. Specifically, the reflected color of the coated glass article 100 at portions 113 and 115 can be relatively colorless at angles of incidence ranging from 0 degrees (normal) to 90 degrees (parallel to the anti-reflective surface 122). The illuminant can include standard illuminants defined by the CIE, including A-series illuminants (representing tungsten lighting), B-series illuminants (simulating daylight), C-series illuminants (simulating daylight), D-series illuminants (representing natural daylight), and F-series illuminants (representing various types of fluorescent lighting). For example, measurements can be made using the International Commission on Illumination D65 illuminant.

[0112] According to one or more embodiments, the first surface reflected color of the coated glass article 100 at the first portion 113 can be defined as a* less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1, as measured normal to the first portion 113, for all angles of incidence from 0 degrees to 90 degrees, and / or a* is at least -10, at least -9, at least -8, at least -7, at least -6, at least -5, at least -4, at least -3, at least -2, or at least -1. The first surface reflected color of the coated glass article 100 at the first portion 113 can be defined as b* less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1 for all angles of incidence from 0 to 90 degrees, and / or b* is at least -10, at least -9, at least -8, at least -7, at least -6, at least -5, at least -4, at least -3, at least -2, or at least -1. According to additional embodiments, the disclosed a* and b* ranges can be measured over an angle of incidence range of 0 to 80, 70, 60, 50, 40, 30, or 20 degrees.

[0113] According to one or more embodiments, the first surface reflected color of the coated glass article 100 at the second portion 115 can be defined as a* less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1, for all angles of incidence measured normal to the second portion 115 from 0 degrees to 90 degrees, and / or a* is at least -10, at least -9, at least -8, at least -7, at least -6, at least -5, at least -4, at least -3, at least -2, or at least -1. The first surface reflected color of the coated glass article 100 at the second portion 115 can be defined as b* less than or equal to 10, less than or equal to 9, less than or equal to 8, less than or equal to 7, less than or equal to 6, less than or equal to 5, less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1 for all angles of incidence from 0 to 90 degrees, and / or b* is at least -10, at least -9, at least -8, at least -7, at least -6, at least -5, at least -4, at least -3, at least -2, or at least -1. According to additional embodiments, the disclosed a* and b* ranges can be measured over an angle of incidence range of 0 to 80, 70, 60, 50, 40, 30, or 20 degrees. In embodiments having the above-described a* and / or b*, the thickness of the optical coating 120 on the second portion 115 is 70% or less (i.e., scaled to 0.7 or less), 65% or less (i.e., scaled to 0.65 or less), 60% or less (i.e., scaled to 0.6 or less), 55% or less (i.e., scaled to 0.55 or less), 50% or less (i.e., scaled to 0.5 or less), 45% or less (i.e., scaled to 0.45 or less), 40% or less (i.e., scaled to 0.4 or less), 35% or less (i.e., scaled to 0.35 or less), or even 30% or less (i.e., scaled to 0.3 or less) of the thickness of the optical coating 120 on the first portion 113.

[0114] According to one or more embodiments, the first surface reflected color of the coated glass article 100 at the first portion 113 is defined as b* < 2.5 for all angles of incidence from 0 degrees to 90 degrees, as measured perpendicular to the first portion 113 of the first major surface 112; and the first surface reflected color of the coated glass article 100 at the second portion 115 is defined as b* < 2.5 for all angles of incidence from 0 degrees to 90 degrees, as measured perpendicular to the second portion 115 of the first major surface 112, where the scaling factor is 0.7 or less.

[0115] According to another embodiment, the first surface reflection color of the coated glass article 100 at the first portion 113 is defined as being measured at the first portion 113 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -10 < a* < 10 and -10 < b* < 10; and the first surface reflection color of the coated glass article 100 at the second portion 115 is defined as being measured at the second portion 115 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -10 < a* < 10 and -10 < b* < 10, where the scaling factor is 0.5 or less.

[0116] According to another embodiment, the first surface reflection color of the coated glass article 100 at the first portion 113 is defined as being measured at the first portion 113 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -2 < a* < 2 and -2 < b* < 2; and the first surface reflection color of the coated glass article 100 at the second portion 115 is defined as being measured at the second portion 115 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -2 < a* < 2 and -2 < b* < 2, where the scaling factor is 0.7 or less.

[0117] According to another embodiment, the first surface reflection color of the coated glass article 100 at the first portion 113 is defined as being measured at the first portion 113 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -10 < a* < 10 and -10 < b* < 10; and the first surface reflection color of the coated glass article 100 at the second portion 115 is defined as being measured at the second portion 115 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -10 < a* < 10 and -10 < b* < 10, where the scaling factor is 0.6 or less.

[0118] According to another embodiment, the first surface reflection color of the coated glass article 100 at the first portion 113 is defined as being measured at the first portion 113 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, b* < 4; and the first surface reflection color of the coated glass article 100 at the second portion 115 is defined as being measured at the second portion 115 perpendicular to the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, b* < 4, where the scaling factor is 0.6 or less.

[0119] According to another embodiment, the first surface reflection color of the coated glass article 100 at the first portion 113 is defined as being measured perpendicular to the first portion 113 of the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -6 < a* < 6 and -10 < b* < 10; and the first surface reflection color of the coated glass article 100 at the second portion 115 is defined as being measured perpendicular to the second portion 115 of the first major surface 112, and for all angles of incidence from 0 degrees to 90 degrees, -6 < a* < 6 and -10 < b*, where the scaling factor is 0.35 or less.

[0120] According to some embodiments, the coated glass article 100 may exhibit color and reflectance uniformity related to thickness variations of the optical coating 120, which variations are caused by the line-of-sight layer, film, and optical structure deposition methods, as well as non-planar portions of the glass substrate 110, such as those associated with a glass substrate 110 having flat, angled, or curved regions. For optical film structure thickness scaling factors in the range of 70% to 100%, 60% to 100%, 50% to 100%, 40% to 100%, or even 35% to 100%, these coated glass articles 100 may exhibit a color shift of the first surface reflection and / or double-surface transmission that is less than 4, less than 3, or even less than 2, as given by √(a* 2 + b* 2 )

[0121] In some embodiments, the coated glass article 100 may exhibit a color shift of the first surface reflection and / or double-surface transmission that is greater than about 12, greater than about 16, or even greater than about 18 at at least one angle of incidence from 0 degrees to 90 degrees, as given by √(a* 2 + b* 2 )

[0122] As previously mentioned, the coated glass article 100 of the present disclosure (see Figure 18) include an optical coating 120 having low reflectivity and controlled color. The optical coating 120 in these coated glass articles 100 can be optimized to provide an ideal combination of hardness, reflectivity, color, and color shift over a range of viewing angles. These ideal combinations are maintained when the optical coating 120 is at its original design thickness, and when all layers in the coating are thinned by a scaling factor corresponding to coating thinning, which can occur during various vacuum deposition techniques (e.g., reactive sputtering, thermal evaporation, CVD, PECVD, etc.) due to line-of-sight effects in the coating process.

[0123] Further regarding the residual compressive stress and elastic modulus levels (as well as the hardness level) of the optical coating 120, these properties can be controlled by adjusting the stoichiometry and / or thickness of the low RI layer 130A, the high RI layer 130B, and the scratch-resistant layer 150. In embodiments, the residual compressive stress and elastic modulus levels (as well as the hardness level) exhibited by the optical coating 120 can be controlled by adjusting the processing conditions for sputtering the layers of the optical coating 120, particularly the high RI layer 130B and the scratch-resistant layer 150. For example, in some implementations, a reactive sputtering process can be employed to deposit the high RI layer 130B comprising a silicon-containing nitride or silicon-containing oxynitride. Furthermore, these high RI layers 130B can be deposited by applying power to a silicon sputtering target in a reactive gas environment comprising argon (e.g., at a flow rate of 50 to 150 sccm), nitrogen (e.g., at a flow rate of 200 to 250 sccm), and oxygen, with the residual compressive stress and elastic modulus levels primarily determined by the selected oxygen flow rate. For example, a relatively low oxygen flow rate (eg, 45 sccm) can be used according to the aforementioned argon and nitrogen flow conditions to produce SiO x N y The stoichiometric high RI layer 130B is such that the optical coating 120 thereof exhibits a residual compressive stress of about 942 MPa, a hardness of 17.8 GPa, and an elastic modulus of 162.6 GPa. As another example, a relatively high oxygen flow rate (e.g., 65 sccm) can be used according to the aforementioned argon and nitrogen flow conditions to produce an optical coating having SiO x N y The stoichiometric high RI layer 130B results in the optical coating 120 exhibiting a residual compressive stress of approximately 913 MPa, a hardness of 16.4 GPa, and an elastic modulus of 148.4 GPa. Thus, the stoichiometry of the optical coating 120 (particularly its high RI layer 130B and scratch-resistant layer 150) can be controlled to achieve target residual compressive stress and elastic modulus levels, which unexpectedly correlate to advantageously high average failure stress levels (e.g., greater than or equal to 700 MPa) in the coated glass article 100.

[0124] According to some implementations, the coated article can exhibit a first surface (i.e., through one major surface of the glass substrate 110) reflected color of less than 10, less than 8, less than 6, less than 4, less than 3, or even less than 2 under a D65 illuminant, measured at normal incidence, all angles of incidence from 0 to 10 degrees, or from 0 to 90 degrees, as expressed as √(a* 2 +b* 2 ). For example, the coated glass article 100 can exhibit a reflected color of less than 10, 9, 8, 7, 6, 5, 4, 3.75, 3.5, 3.25, 3, 2.75, 2.5, 2.25, 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1, or even less, measured at normal incidence, all angles of incidence from 0 to 10 degrees, or from 0 to 90 degrees.

[0125] The disclosed coated articles can be used to protect and / or cover displays, camera lenses, sensors and / or light source components within or as part of electronic devices, as well as to protect other components (such as buttons, speakers, microphones, etc.). These transparent articles with protective functions use optical coatings placed on glass-ceramic substrates so that the articles exhibit a combination of high hardness, high damage resistance and ideal optical properties (including high photopic transmittance and low transmittance color). The optical coating may include a scratch-resistant layer located at any different position within the structure. In addition, the optical coating of these articles may include a plurality of alternating high refractive index layers and low refractive index layers, wherein each high refractive index layer and scratch-resistant layer comprises a nitride or oxynitride, and each low refractive index layer comprises an oxide.

[0126] The coated glass article 100 can be substantially optically clear, transparent, and free of light scattering elements. In such embodiments, the coated glass article 100 can exhibit an average light transmittance of about 85% or greater, about 86% or greater, about 87% or greater, about 88% or greater, about 89% or greater, about 90% or greater, about 91% or greater, or about 92% or greater over the optical wavelength regime. In one or more alternative embodiments, the coated glass article 100 can be opaque or exhibit an average light transmittance of less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0.5% over the optical wavelength regime. In some embodiments, these light reflectance and transmittance values ​​can be total reflectance or total transmittance (considering reflectance or transmittance on both major surfaces of the substrate) or can be observed on a single side of the substrate (i.e., observed only on the anti-reflective surface 122, without considering the opposing surface). Unless otherwise noted, the average reflectivity or transmittance of an individual substrate is measured at an incident illumination angle of 0 degrees relative to the substrate major surface 112 (however, such measurements may be provided at incident illumination angles of 45 degrees or 60 degrees). The glass substrate 110 may optionally be a color such as white, black, red, blue, green, yellow, orange, etc.

[0127] In one or more embodiments, the glass substrate 110 may comprise glass. In one or more embodiments, the glass substrate 110 may be a lithium aluminosilicate glass composition. IC ) of a lithium aluminosilicate glass composition. In some embodiments, the glass composition is characterized by a K of at least 0.70 MPa√m IC Fracture toughness values. The glasses described herein are able to achieve these fracture toughness values ​​without the inclusion of additives such as Ta2O5, HfO2, La2O3, and Y2O3, which improve fracture toughness but are expensive and may have limited commercial availability. In this regard, the glasses disclosed herein provide comparable or improved performance while reducing manufacturing costs.

[0128] In the glass compositions described herein, SiO2 is the largest component and, therefore, the primary component of the glass network structure formed by the glass composition. Pure SiO2 has a relatively low CTE value. However, pure SiO2 has a high melting point. Therefore, if the concentration of SiO2 in the glass composition is too high, the formability of the glass composition may be reduced because a higher concentration of SiO2 increases the difficulty of melting the glass, which in turn has a negative impact on the formability of the glass. If the concentration of SiO2 in the glass composition is too low, the chemical durability of the glass may be reduced, and the glass may be susceptible to surface damage during post-molding processing. In embodiments, the concentration of SiO2 in the glass composition may be in the following ranges: 50.0 to 70.0 mol%, 50.0 to 67.0 mol%, 50.0 to 65.0 mol%, 50.0 to 63.0 mol%, 50.0 to 60.0 mol%, 55.0 to 70.0 mol%, 55.0 to 67.0 mol%, 55.0 to 65.0 mol%, 55.0 to 64.0 mol%, 55.0 to 63.0 mol%, 55.0 to 62.0 mol%, 55.0 to 61.0 mol%, 55.0 to 60.0 mol%, 55.0 to 59.0 mol%, 56.0 to 70.0 mol%, 56.0 to 67.0 mol%, % 57.0 to 65.0 mol%, 57.0 to 64.0 mol%, 57.0 to 63.0 mol%, 57.0 to 62.0 mol%, 57.0 to 61.0 mol%, 57.0 to 60.0 mol%, 57.0 to 59.0 mol%, 57.0 to 70.0 mol%, 57.0 to 67.0 mol%, 57.0 to 65.0 mol%, 57.0 to 64.0 mol%, 57.0 to 63.0 mol%, 57.0 to 62.0 mol%, 57.0 to 61.0 mol%, 57.0 to 60.0 mol%, or 57.0 to 59.0 mol%, or any and all subranges formed from any of these endpoints.

[0129] The glass composition may include Al2O3. Similar to SiO2, Al2O3 can act as a glass network former. Al2O3, due to its tetrahedral coordination in a glass melt formed from the glass composition, can increase the viscosity of the glass composition, thereby reducing the formability of the glass composition when the amount of Al2O3 is too high. However, when the concentration of Al2O3 in the glass composition is balanced with the concentration of SiO2 and the concentration of alkali metal oxides, Al2O3 can lower the liquidus temperature of the glass melt, thereby increasing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes. Including Al2O3 in the glass composition achieves the high fracture toughness values ​​described herein. In an embodiment, the concentration of Al2O3 in the glass composition may be in the following ranges: 10.0 to 25.0 mol%, 10.0 to 23.0 mol%, 10.0 to 20.0 mol%, 10.0 to 19.0 mol%, 10.0 to 18.0 mol%, 12.0 to 25.0 mol%, 12.0 to 23.0 mol%, 12.0 to 20.0 mol%, 12.0 to 19.0 mol%, 12.0 to 18.0 mol%, 13.0 to 25.0 mol%, 13.0 to 23.0 mol%, 13.0 to 20.0 mol%, 13.0 to 19.0 mol%, 13.0 to 18.0 mol%, 14.0 to 25.0 mol%, 14.0 to 23.0 mol%, 14.0 to 19.0 mol%, 14.0 to 18.0 mol%. % 17.0 to 25.0 mol%, 17.0 to 23.0 mol%, 17.0 to 20.0 mol%, 17.0 to 19.0 mol%, or 17.0 to 18.0 mol%, or any and all subranges formed from any of these endpoints. In embodiments, the concentration of Al2O3 in the glass composition may be greater than or equal to 10.0 mol%, greater than or equal to 11.0 mol%, greater than or equal to 12.0 mol%, greater than or equal to 13.0 mol%, greater than or equal to 14.0 mol%, greater than or equal to 15.0 mol%, greater than or equal to 16.0 mol%, or greater than or equal to 17.0 mol%.

[0130] The glass composition may include Li2O. Including Li2O in the glass composition allows for better control of the ion exchange process and further lowers the softening point of the glass, thereby improving the manufacturability of the glass. The presence of Li2O in the glass composition also allows for a parabolic stress profile. The Li2O in the glass composition achieves the high fracture toughness values ​​described herein. In an embodiment, the glass composition may include 5.0 to 15.0 mol% Li2O. In an embodiment, the glass composition may include 5.0 to 10.0 mol% Li2O. In an embodiment, the glass composition may include 6.0 to 9.0 mol% Li2O. In an embodiment, the concentration of Li2O in the glass composition may be in the following ranges: 5.0 to 15.0 mol%, 5.0 to 10.0 mol%, 5.0 to 9.0 mol%, 5.0 to 8.5 mol%, 5.0 to 8.0 mol%, 6.0 to 15.0 mol%, 6.0 to 10.0 mol%, 6.0 to 9.0 mol%, 6.0 to 8.5 mol%, 6.0 to 8.0 mol%, 6.0 to 7.5 mol%, 6.0 to 7.0 mol%, 6.5 to 15.0 mol%, % or less, or less than or equal to 15.0 mol%, less than or equal to 10.0 mol%, less than or equal to 9.5 mol%, less than or equal to 9.0 mol%, less than or equal to 8.5 mol%, or less than or equal to 8.0 mol%, or less than or equal to 8.0 mol%, or less than or equal to 15.0 mol%, less than or equal to 10.0 mol%, less than or equal to 9.5 mol%, less than or equal to 9.0 mol%, less than or equal to 8.5 mol%, or less than or equal to 8.0 mol%.

[0131] The glass compositions described herein may include Na2O. Na2O may contribute to the ion exchangeability of the glass composition and improve the formability of the glass composition, thereby improving the manufacturability of the glass composition. However, if too much Na2O is added to the glass composition, the CTE may be too low and the melting point may be too high. Additionally, if the amount of Na2O included in the glass is too high relative to the amount of Li2O, the ability of the glass to achieve deep compression during ion exchange may be reduced. In an embodiment, the glass composition may include 1.0 to 15.0 mol% Na2O. In an embodiment, the glass composition may include 4.0 to 10.0 mol% Na2O. In an embodiment, the glass composition may include 5.0 to 9.0 mol% Na2O. In embodiments, the concentration of Na2O in the glass composition may be in the following ranges: 1.0 to 15.0 mol%, 1.0 to 10.0 mol%, 3.0 to 15.0 mol%, 3.0 to 10.0 mol%, 4.0 to 15.0 mol%, 4.0 to 10.0 mol%, 4.0 to 9.5 mol%, 4.0 to 9.0 mol%, 4.5 to 15.0 mol%, 4.5 to 10.0 mol%, 4.5 to 9.5 mol%, 4.5 to 9.0 mol%, 5.0 to 15 mol%, 5.0 to 10.0 mol%, 5.0 to 9.5 mol%, 5.0 to 9.0 mol%, 5.5 to 15.0 mol%, 5.5 to 10 ...%. % or 8.0 to 10.0 mol%, or any and all subranges formed from any of these endpoints. In embodiments, the concentration of Na 2 O in the glass composition may be less than or equal to 15.0 mol %, less than or equal to 10.0 mol %, less than or equal to 9.5 mol %, or less than or equal to 9.0 mol %.

[0132] The glass compositions described herein may include PO. Including PO increases the diffusivity of ions in the glass, thereby increasing the speed of the ion exchange process. If the composition includes too much PO, the amount of compressive stress imparted during the ion exchange process may be reduced, and volatility at the free surface during manufacturing may increase to undesirable levels. In an embodiment, the glass composition may include 0.0 to 5.0 mol% PO. In an embodiment, the glass composition may include 0.3 to 3.0 mol% PO. In an embodiment, the glass composition may include 0.5 to 2.5 mol% PO. In embodiments, the concentration of P2O5 in the glass composition may be in the following ranges: 0.0 to 5.0 mol%, 0.0 to 4.0 mol%, 0.0 to 3.0 mol%, 0.0 to 2.5 mol%, 0.0 to 2.3 mol%, 0.0 to 2.0 mol%, 0.0 to 1.7 mol%, 0.0 to 1.5 mol%, 0.3 to 5.0 mol%, 0.3 to 4.0 mol%, 0.3 to 3.0 mol%, 0.3 to 2.5 mol%, 0.3 to 2.3 mol%, 0.3 to 2.0 mol%, 0.3 to 1.7 mol%, 0.3 to 1.5 mol%, 0.5 to 5.0 mol%, 0.5 to 4.0 mol%, 0.5 to 3.0 mol%, 0.5 to 2.5 mol%. %, 0.5 to 2.3 mol%, 0.5 to 2.0 mol%, 0.5 to 1.7 mol%, 0.5 to 1.5 mol%, 0.7 to 5.0 mol%, 0.7 to 4.0 mol%, 0.7 to 3.0 mol%, 0.7 to 2.5 mol%, 0.7 to 2.3 mol%, 0.7 to 2.0 mol%, 0.7 to 1.7 mol%, 0.7 to 1.5 mol%, 1.0 to 5.0 mol%, 1.0 to 4.0 mol%, 1.0 to 3.0 mol%, 1.0 to 2.5 mol%, 1.0 to 2.3 mol%, 1.0 to 2.0 mol%, 1.0 to 1.7 mol%, or 1.0 to 1.5 mol%, or any and all subranges derived from any of these endpoints. In an embodiment, the glass composition may include less than or equal to 4.0 mol% PO. In embodiments, the concentration of P2O5 in the glass composition may be less than or equal to 5.0 mol%, less than or equal to 4.5 mol%, less than or equal to 4.0 mol%, less than or equal to 3.5 mol%, less than or equal to 3.0 mol%, less than or equal to 2.5 mol%, less than or equal to 2.0 mol%, or less than or equal to 1.5 mol%.

[0133] The glass compositions described herein may include B2O3. Including B2O3 improves the fracture toughness of the glass. Specifically, the glass composition includes boron in a trigonal configuration, which increases the Knoop scratch threshold and fracture toughness of the glass. If the composition includes too much B2O3, the amount of compressive stress imparted during the ion exchange process may be reduced, and volatility at the free surface during manufacturing may increase to undesirable levels. In an embodiment, the glass composition may include 0.0 to 10.0 mol% B2O3. In an embodiment, the glass composition may include 1.0 to 7.0 mol% B2O3. In an embodiment, the glass composition may include 2.0 to 6.0 mol% B2O3. In an embodiment, the concentration of B2O3 in the glass composition may be in the following ranges: 0.0 to 10.0 mol%, 0.0 to 9.0 mol%, 0.0 to 8.0 mol%, 0.0 to 7.5 mol%, 0.0 to 7.0 mol%, 0.0 to 6.5 mol%, 0.0 to 6.0 mol%, 0.0 to 5.5 mol%, 0.0 to 5.0 mol%, 0.0 to 4.5 mol%, 0.5 to 10.0 mol%, 0.5 to 9.0 mol%, 0.5 ...5 mol%, 0.0 to 7.5 mol%, 0.0 to .5 to 7.5 mol%, 0.5 to 7.0 mol%, 0.5 to 6.5 mol%, 0.5 to 6.0 mol%, 0.5 to 5.5 mol%, 0.5 to 5.0 mol%, 0.5 to 4.5 mol%, 1.0 to 10.0 mol%, 1.0 to 9.0 mol%, 1.0 to 8.0 mol%, 1.0 to 7.5 mol%, 1.0 to 7.0 mol%, 1.0 to 6.5 mol%, 1.0 to 6.0 mol%, 1.0 to 5.5 mol%, 1.0 to 5. 0 mol%, 1.0 to 4.5 mol%, 1.5 to 10.0 mol%, 1.5 to 9.0 mol%, 1.5 to 8.0 mol%, 1.5 to 7.5 mol%, 1.5 to 7.0 mol%, 1.5 to 6.5 mol%, 1.5 to 6.0 mol%, 1.5 to 5.5 mol%, 1.5 to 5.0 mol%, 1.5 to 4.5 mol%, 2.0 to 10 mol%, 2.0 to 9.0 mol%, 2.0 to 8.0 mol%, 2.0 to 7.5 mol%, 2.0 to 7.0 mol%, 2.0 to 6.5 mol%, 2.0 to 6.0 mol%, 2.0 to 5.5 mol%, 2.0 to 5.0 mol%, 2.0 to 4.5 mol%, 2.5 to 10.0 mol%, 2.5 to 9.0 mol%, 2.5 to 8.0 mol%, 2.5 to 7.5 mol%, 2.5 to 7.0 mol%, 2.5 to 6.5 mol%, 0.0 to 6.0 mol%, 0.0 to 5.5 mol%, 2.5 to 5.0 mol%, 2.5 to 4.5 mol%, 3.0 to 10.0 mol%, 3.0 to 9.0 mol%, 3.0 to 8.0 mol%, 3.0 to 7.5 mol%, 3.0 to 7.0 mol%, 3.0 to 6.5 mol%, 3.0 to 6.0 mol%, 3.0 to 5.5 mol%, 3.0 to 5.0 mol%, 3.0 to 4.5 mol%, 3.5 to 10.0 mol%, 3.5 to 9.0 mol%, 3.5 to 8.0 mol%, 3.5 to 7.5 mol%, 3.5 to 7.0 mol%, % , 3.5 to 6.5 mol%, 3.5 to 6.0 mol%, 3.5 to 5.5 mol%, 3.5 to 5.0 mol%, 3.5 to 4.5 mol%, 4.0 to 10.0 mol%, 4.0 to 9.0 mol%, 4.0 to 8.0 mol%, 4.0 to 7.5 mol%, 4.0 to 7.0 mol%, 4.0 to 6.5 mol%, 4.0 to 6.0 mol%, 4.0 to 5.5 mol%, or 4.0 to 5.0 mol%, or any and all subranges formed therefrom. In an embodiment, the concentration of B2O3 in the glass composition may be greater than or equal to 0.5 mol%, greater than or equal to 1.0 mol%, greater than or equal to 1.5 mol%, greater than or equal to 2.0 mol%, greater than or equal to 2.5 mol%, greater than or equal to 3.0 mol%, greater than or equal to 3.5 mol%, or greater than or equal to 4.0 mol%.

[0134] The glass compositions described herein may include TiO2. Excessive TiO2 inclusion in the glass composition may cause the glass to be susceptible to devitrification and / or exhibit undesirable coloration, as well as undesirable shifts in the liquidus. Including TiO2 in the glass composition prevents undesirable discoloration of the glass when exposed to intense UV light, such as during post-processing. In an embodiment, the glass composition includes TiO2 in an amount from greater than 0 mol% to less than 1 mol%, such as from greater than or equal to 0.1 mol% to less than or equal to 1.0 mol%, from greater than or equal to 0.2 mol% to less than or equal to 0.9 mol%, from greater than or equal to 0.3 mol% to less than or equal to 0.8 mol%, from greater than or equal to 0.4 mol% to less than or equal to 0.7 mol%, from greater than or equal to 0.5 mol% to less than or equal to 0.6 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.2 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.5 mol%, and all ranges and subranges therebetween.

[0135] The glass composition may include K2O. Including K2O in the glass composition increases the diffusivity of potassium in the glass, enabling a deeper depth of compressive stress spike (DOL) to be achieved in a shorter amount of ion exchange time. SP). If too much KO is included in the composition, the amount of compressive stress imparted during the ion exchange process may be reduced. In an embodiment, the glass composition may include 0.0 to 1.0 mol% KO. In an embodiment, the glass composition may include 0.0 to 0.5 mol% KO. In an embodiment, the glass composition may include 0.0 to 0.4 mol% KO. In an embodiment, the concentration of KO in the glass composition may be in the range of 0.0 to 1.0 mol%, 0.0 to 0.5 mol%, 0.0 to 0.4 mol%, 0.0 to 0.3 mol%, 0.0 to 0.2 mol%, or 0.0 to 0.1 mol%, or any and all subranges formed from any of these endpoints. In embodiments, the glass composition may include less than or equal to 1.0 mol % K 2 O, less than or equal to 0.5 mol % K 2 O, less than or equal to 0.4 mol % K 2 O, less than or equal to 0.3 mol % K 2 O, less than or equal to 0.2 mol % K 2 O, or less than or equal to 0.1 mol % K 2 O.

[0136] The glass compositions described herein may include MgO. MgO can reduce the viscosity of the glass, which enhances the formability and manufacturability of the glass. Including MgO in the glass composition can also improve the strain point and Young's modulus of the glass composition. However, if too much MgO is added to the glass composition, the liquidus viscosity may be too low to be compatible with ideal forming techniques. Adding too much MgO may also increase the density and CTE of the glass composition to undesirable levels. Including MgO in the glass composition also helps achieve the high fracture toughness values ​​described herein. In an embodiment, the glass composition includes MgO in an amount from greater than or equal to 0 mol% to less than or equal to 4 mol%, such as greater than or equal to 0 mol% to less than or equal to 4.0 mol%, greater than or equal to 0.5 mol% to less than or equal to 3.5 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1.0 mol% to less than or equal to 3.0 mol%, greater than or equal to 1.5 mol% to less than or equal to 2.5 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2.0 mol% to less than or equal to 3 mol%, greater than or equal to 0.1 mol% to less than or equal to 1 mol%, and all ranges and subranges therebetween. In an embodiment, the glass composition is substantially free of or free of MgO. As used herein, the term "substantially free" means that the component (e.g., MgO) (or components, such as Ta2O5, HfO2, La2O3, and Y2O3) is not purposefully added as a component (or components) of the batch material, even though the component (or components) may be present in the final glass composition as a contaminant (or contaminants) in a very small amount (e.g., less than 0.1 mol%).

[0137] The glass compositions described herein may include CaO. CaO can reduce the viscosity of the glass, which can enhance formability, strain point, and Young's modulus. However, if too much CaO is added to the glass composition, the density and CTE of the glass composition may increase to undesirable levels, and the ion exchangeability of the glass may also be undesirably hindered. Including CaO in the glass composition also helps achieve the high fracture toughness values ​​described herein. In embodiments, the glass composition includes CaO in an amount from greater than or equal to 0 mol% to less than or equal to 3 mol%, such as from greater than 0 mol% to less than or equal to 3.0 mol%, from greater than or equal to 0.5 mol% to less than or equal to 2.5 mol%, from greater than or equal to 1 mol% to less than or equal to 2 mol%, from greater than or equal to 1.0 mol% to less than or equal to 2.0 mol%, from greater than or equal to 1.5 mol% to less than or equal to 2.0 mol%, from greater than or equal to 1 mol% to less than or equal to 2 mol%, and all ranges and subranges therebetween. In embodiments, the glass composition is substantially free of or free of CaO.

[0138] The glass compositions described herein may include SrO. SrO can reduce the viscosity of the glass, which can enhance formability, strain point, and Young's modulus. However, if too much SrO is added to the glass composition, the density and CTE of the glass composition may increase to undesirable levels, and the ion exchangeability of the glass may be undesirably hindered. Including SrO in the glass composition also helps achieve the high fracture toughness values ​​described herein. In an embodiment, the glass composition includes SrO in an amount from greater than or equal to 0 mol% to less than or equal to 4 mol%, such as greater than or equal to 0 mol% to less than or equal to 4.0 mol%, greater than or equal to 0.5 mol% to less than or equal to 3.5 mol%, greater than or equal to 1 mol% to less than or equal to 3 mol%, greater than or equal to 1.0 mol% to less than or equal to 3.0 mol%, greater than or equal to 1.5 mol% to less than or equal to 2.5 mol%, greater than or equal to 1 mol% to less than or equal to 2 mol%, greater than or equal to 2.0 mol% to less than or equal to 3 mol%, greater than or equal to 0.5 mol% to less than or equal to 2 mol%, and all ranges and subranges therebetween. In an embodiment, the glass composition is substantially free of or free of SrO.

[0139] The glass compositions described herein may include ZnO. ZnO can reduce the viscosity of the glass, which can enhance formability, strain point, and Young's modulus. However, if too much ZnO is added to the glass composition, the density and CTE of the glass composition may increase to undesirable levels. Including ZnO in the glass composition also helps achieve the high fracture toughness values ​​described herein and provides protection against UV-induced discoloration. In embodiments, the glass composition includes ZnO in an amount from greater than or equal to 0 mol% to less than or equal to 1 mol%, such as from greater than or equal to 0 mol% to less than or equal to 1.0 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.9 mol%, from greater than or equal to 0.2 mol% to less than or equal to 0.8 mol%, from greater than or equal to 0.3 mol% to less than or equal to 0.7 mol%, from greater than or equal to 0.4 mol% to less than or equal to 0.6 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.5 mol%, from greater than or equal to 0 mol% to less than or equal to 0.3 mol%, and all ranges and subranges therebetween. In embodiments, the glass composition is substantially free or free of ZnO.

[0140] The glass composition may optionally include one or more fining agents. In an embodiment, the fining agent may include, for example, SnO2. In an embodiment, SnO2 may be present in the glass composition in an amount less than or equal to 0.2 mol%, such as from greater than or equal to 0 mol% to less than or equal to 0.2 mol%, from greater than or equal to 0 mol% to less than or equal to 0.1 mol%, from greater than or equal to 0 mol% to less than or equal to 0.05 mol%, from greater than or equal to 0.1 mol% to less than or equal to 0.2 mol%, and all ranges and sub-ranges therebetween. In some embodiments, the glass composition may be substantially free of or free of SnO2. In an embodiment, the glass composition may be substantially free of one or both of arsenic and antimony. In other embodiments, the glass composition may be free of one or both of arsenic and antimony.

[0141] The glass compositions described herein may further include Fe2O3. In embodiments, the concentration of Fe2O3 in the glass composition may be 0.0 to 1.0 mol%, 0.0 to 0.5 mol%, 0.0 to 0.4 mol%, 0.0 to 0.3 mol%, 0.0 to 0.2 mol%, or 0.0 to 0.1 mol%, or any and all subranges formed from any of these endpoints. In embodiments, the concentration of Fe2O3 in the glass composition may be less than or equal to 0.1 mol%. In embodiments, the concentration of Fe2O3 in the glass composition may be greater than 0.0 mol% to less than or equal to 0.1 mol%. In embodiments, the glass composition may be substantially free of or free of Fe2O3.

[0142] In embodiments, the glass composition can be substantially free of or free of at least one of Ta2O5, HfO2, La2O3, and Y2O3. In embodiments, the glass composition can be substantially free of or free of Ta2O5, HfO2, La2O3, and Y2O3. While these components can improve the fracture toughness of the glass when included, there are cost and supply limitations that make their use for commercial purposes undesirable. In other words, the ability of the glass compositions described herein to achieve high fracture toughness values ​​without including Ta2O5, HfO2, La2O3, and Y2O3 provides cost and manufacturability advantages.

[0143] The glass compositions described herein can be described in terms of a molar ratio of lithium to sodium (Li2O / Na2O). A high Li2O / Na2O molar ratio allows for a deep depth of compression (DOC) to be achieved when the glass composition is ion-exchanged. The enhanced DOC capability attributable to the high Li2O / Na2O molar ratio allows ion-exchanged articles formed from the glass composition to exhibit improved drop performance, particularly on rough surfaces. In an embodiment, the glass composition is characterized by a Li2O / Na2O molar ratio of greater than or equal to 1.2 to less than or equal to 2.0, such as greater than or equal to 1.3 to less than or equal to 1.9, greater than or equal to 1.4 to less than or equal to 1.8, greater than or equal to 1.5 to less than or equal to 1.7, greater than or equal to 1.6 to less than or equal to 2.0, and all ranges and subranges therebetween.

[0144] The physical properties of the glass compositions disclosed above will now be discussed.

[0145] The glass compositions according to the embodiments have high fracture toughness. Without wishing to be bound by any particular theory, the high fracture toughness may impart improved drop performance to the glass compositions. The high fracture toughness of the glass compositions described herein increases the damage resistance of the glass and allows for higher levels of stress (characterized by central tension) to be imparted to the glass through ion exchange without the glass becoming brittle. As used herein, fracture toughness (K 1C ) represents the ability of a glass composition to resist fracture. Fracture toughness is measured on a non-strengthened glass article, such as K before the glass article is subjected to ion exchange (IOX) treatment. 1C The fracture toughness test method described herein is not suitable for glass that has been exposed to IOX treatment. Nevertheless, measurements made on the corresponding underlying glass substrate (not IOX treated) provide valuable information about the properties of the glass after IOX treatment. 1CThe chevron notched short bar (CNSB) method is disclosed in Reddy, KPR et al., “Fracture Toughness Measurement of Glass and Ceramic Materials Using Chevron-Notched Specimens”, Journal of the American Ceramic Society (J.Am.Ceram.Soc.), 71[6], C-310-C-313 (1988), except that Y* m Calculated using Equation 5 of Bubsey, RT et al., "Closed-Form Expressions for Crack-Mouth Displacement and Stress Intensity Factors for Chevron-Notched Short Bar and Short Rod Specimens Based on Experimental Compliance Measurements," NASA Technical Memorandum 83796, pp. 1-30 (October 1992). Unless otherwise noted, all fracture toughness values ​​are measured by the V-notched short bar (CNSB) method.

[0146] In the examples, the K of the glass composition measured by the V-notch short rod method is 1C The fracture toughness may be greater than or equal to 0.70, greater than or equal to 0.71, greater than or equal to 0.72, greater than or equal to 0.73, greater than or equal to 0.74, greater than or equal to 0.75, greater than or equal to 0.76, greater than or equal to 0.77, greater than or equal to 0.78, greater than or equal to 0.79, or greater than or equal to 0.80. In an embodiment, the K of the glass composition measured by the V-notch short rod method 1C The fracture toughness can be within a range of greater than or equal to 0.70 to less than or equal to 0.80 or greater than or equal to 0.73 to less than or equal to 0.75. It will be appreciated that the fracture toughness can be within subranges formed by any and all of the aforementioned endpoints.

[0147] In one or more embodiments, the glass substrate described herein may have an elastic modulus (Young's modulus) greater than or equal to 72.0 GPa, such as greater than or equal to 73.0 GPa, greater than or equal to 74.0 GPa, greater than or equal to 75.0 GPa, greater than or equal to 76.0 GPa, greater than or equal to 77.0 GPa, greater than or equal to 78.0 GPa, greater than or equal to 79.0 GPa, or even greater than or equal to 80.0 GPa.

[0148] The liquidus viscosity of the glass composition described herein is compatible with manufacturing processes that are particularly suitable for forming thin glass sheets. For example, the glass composition is compatible with downward drawing processes (such as fusion drawing processes or slot drawing processes). The embodiment of the glass substrate 110 can be described as fusion-molded (i.e., fusion drawing processes can be used for molding). The fusion process uses a drawing trough, which has a channel for receiving molten glass raw materials. The channel has a weir that is open at the top along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass overflows the weir. Due to gravity, the molten glass flows downward along the outer surface of the drawing trough as two flowing glass films. These outer surfaces of the drawing trough extend downward and inward so that they combine at the edge below the drawing trough. The two flowing glass films combine at this edge to fuse and form a single flowing glass substrate 110. The fusion of the glass films produces a fusion line in the glass substrate 110, and this fusion line allows the fusion-molded glass substrate 110 to be identified without additionally understanding the manufacturing history. The fusion drawing method provides an advantage in that, because the two glass films flowing through the channel fuse together, neither outer surface of the resulting glass substrate 110 comes into contact with any part of the apparatus. Therefore, the surface properties of the fusion drawn glass substrate 110 are not affected by such contact.

[0149] The glass composition described herein can be selected to have a liquidus viscosity that is compatible with the fusion drawing process. Therefore, the glass composition described herein is compatible with existing forming methods, thereby improving the manufacturability of the glass substrate 110 formed by the glass composition. As used herein, the term "liquidus viscosity" refers to the viscosity of molten glass at the liquidus temperature, wherein the liquidus temperature refers to the temperature at which crystals first appear when the molten glass is cooled from the melting temperature, or the temperature at which the last crystals melt when the temperature is raised from room temperature. Unless otherwise stated, the liquidus viscosity values ​​disclosed in this application are determined by the following method. First, the liquidus temperature of the glass is measured according to ASTM C829-81 (2015), entitled "Standard Practice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method." Next, the viscosity of the glass at the liquidus temperature was measured according to ASTM C965-96 (2012), entitled "Standard Practice for Measuring Viscosity of Glass Above the Softening Point." As used herein, the term "Vogel-Fulcher-Tamman ('VFT') relationship" describes the temperature dependence of viscosity and is represented by the following equation (3):

[0150]

[0151] Where η is the viscosity. To determine VFT A, VFT B and VFT T o The viscosity of the glass composition is measured within a given temperature range. The raw data of viscosity versus temperature are then fitted to the VFT equation by least squares fitting to obtain A, B, and T. o Using these values, the viscosity point at any temperature above the softening point (e.g., 200°C temperature, 35,000°C temperature, and 200,000°C temperature) can be calculated. Unless otherwise specified, the liquidus viscosity and temperature of the glass composition or article are measured before the composition or article is subjected to any ion exchange process or any other strengthening process. Specifically, the liquidus viscosity and temperature of the glass composition or article are measured before the composition or article is exposed to, for example, immersed in, an ion exchange solution.

[0152] In embodiments, the glass composition may have a liquidus viscosity greater than or equal to 50 kP, such as greater than or equal to 55 kP, greater than or equal to 60 kP, greater than or equal to 65 kP, greater than or equal to 70 kP, greater than or equal to 75 kP, or greater than or equal to 75 kP. In embodiments, the glass composition may have a liquidus viscosity greater than or equal to 50 kP to less than or equal to 80 kP, such as greater than or equal to 55 kP to less than or equal to 75 kP, greater than or equal to 60 kP to less than or equal to 70 kP, greater than or equal to 50 kP to less than or equal to 65 kP, greater than or equal to 50 kP to less than or equal to 75 kP, and all ranges and subranges therebetween. Lower liquidus viscosities are associated with higher K IC Values ​​are associated with improved ion exchange capacity, but when the liquidus viscosity is too low, the manufacturability of the glass composition is reduced.

[0153] The glass composition can be described based on the components included therein and the properties exhibited by the glass. In an embodiment, the glass includes SiO2, Al2O3, Li2O, Na2O, P2O5, and B2O3, wherein the Li2O / Na2O molar ratio is greater than or equal to 1.2 and less than or equal to 2.0, the liquidus viscosity is within the range of greater than or equal to 50 kP and less than or equal to 75 kP, and K IC The fracture toughness is greater than or equal to 0.75 MPa√m.

[0154] In one or more embodiments, the glass compositions described herein can form a glass substrate 110 that exhibits an amorphous microstructure and can be substantially free of crystals or crystallites. In other words, the glass substrate 110 formed from the glass compositions described herein can include no glass-ceramic material.

[0155] According to the convention commonly used in the art, compressive stress or compression stress is expressed as negative (<0) stress, and tensile stress or tensile stress is expressed as positive (>0) stress. However, throughout this specification, CS is expressed as a positive or absolute value, that is, as described herein, CS=|CS|. The compressive stress (CS) has a maximum value at or near the surface of the glass substrate 110, and CS varies with the distance d from the surface as a function. The compressive stress (including surface CS) can be measured by a surface stress meter (FSM) using commercially available instruments, such as the FSM-6000 manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely on accurate measurement of the stress optical coefficient (SOC) associated with the birefringence of the glass. SOC is in turn measured according to Procedure C (Glass Disc Method) described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," the contents of which are incorporated herein by reference in their entirety.

[0156] In an embodiment, the CS of the glass substrate 110 is greater than or equal to 500 MPa and less than or equal to 1500 MPa, such as greater than or equal to 550 MPa and less than or equal to 1500 MPa, greater than or equal to 600 MPa and less than or equal to 1500 MPa, greater than or equal to 650 MPa and less than or equal to 1450 MPa, greater than or equal to 700 MPa and less than or equal to 1400 MPa, greater than or equal to 750 MPa and less than or equal to 1350 MPa, greater than or equal to 800 MPa and less than or equal to 1500 MPa, or greater than or equal to 1500 MPa. The present invention also includes but is not limited to: greater than or equal to 1300 MPa, greater than or equal to 850 MPa to less than or equal to 1250 MPa, greater than or equal to 900 MPa to less than or equal to 1200 MPa, greater than or equal to 950 MPa to less than or equal to 1150 MPa, greater than or equal to 1000 MPa to less than or equal to 1150 MPa, greater than or equal to 1050 MPa to less than or equal to 1500 MPa, greater than or equal to 1200 MPa to less than or equal to 1300 MPa, and all ranges and subranges between the foregoing values.

[0157] In the embodiment, Na + and K + ion exchanged into the glass substrate 110, and Na + The depth of ion diffusion into the glass substrate 110 is greater than K + ions are deeper. K +The depth of penetration of ions ("potassium DOL") is different from DOC because it represents the depth of potassium penetration caused by the ion exchange process. For the articles described herein, the potassium DOL is generally less than the DOC. The potassium DOL is measured using a surface stress gauge, such as the commercially available FSM-6000 surface stress gauge manufactured by Orihara Seisakusho Co., Ltd. (Japan), which relies on accurate measurement of the stress optical coefficient (SOC), as described above with reference to the CS measurement. The potassium DOL can be defined as the depth of the compressive stress peak (DOL SP ), where the stress distribution transitions from a steep peak region to a less steep deep region. The deep region extends from the bottom of the peak to the compression depth. SP It can be greater than or equal to 3 μm to less than or equal to 12 μm, such as greater than or equal to 4 μm to less than or equal to 11 μm, greater than or equal to 5 μm to less than or equal to 10 μm, greater than or equal to 6 μm to less than or equal to 9 μm, greater than or equal to 7 μm and less than or equal to 8 μm, and all ranges and sub-ranges between the foregoing values.

[0158] The compressive stresses of the two major surfaces are balanced by the storage tension in the central area of ​​the glass substrate. The maximum central tension (CT) and DOC values ​​can be measured using a scattered light polariscope (SCALP) technique known in the art. The refractive near field (RNF) method or SCALP can be used to determine the stress distribution of the glass substrate 110. When the stress distribution is measured using the RNF method, the maximum CT value provided by SCALP is used in the RNF method. In particular, the stress distribution determined by the RNF is force balanced and calibrated to the maximum CT value provided by the SCALP measurement. The RNF method is described in U.S. Patent No. 8,854,623, entitled "Systems and methods for measuring a profile characteristic of a glass sample," which is incorporated herein by reference in its entirety. Specifically, the RNF method includes placing a glass substrate 110 near a reference block, generating a polarization-switching beam that switches between orthogonal polarizations at a rate between 1 Hz and 50 Hz, measuring the amount of power in the polarization-switching beam and generating a polarization-switching reference signal, wherein the measured amount of power in each orthogonal polarization is within 50% of each other. The method further includes transmitting the polarization-switching beam through the glass sample and the reference block into different depths of the glass sample, and then relaying the transmitted polarization-switching beam to a signal photodetector using a relay optical system, wherein the signal photodetector generates a polarization-switching detector signal. The method also includes dividing the detector signal by the reference signal to form a normalized detector signal, and determining a distribution characteristic of the glass sample based on the normalized detector signal.

[0159] The maximum CT value measurement is an indicator of the total amount of stress stored in the strengthened article due to the force balance described above. For this reason, the ability to achieve higher CT values ​​correlates with the ability to achieve higher degrees of strengthening and improved performance. In embodiments, the maximum CT of the glass substrate 110 may be greater than or equal to 20 MPa, such as greater than or equal to 30 MPa, greater than or equal to 40 MPa, greater than or equal to 50 MPa, greater than or equal to 60 MPa, greater than or equal to 70 MPa, greater than or equal to 80 MPa, greater than or equal to 90 MPa, greater than or equal to 100 MPa, greater than or equal to 110 MPa, greater than or equal to 120 MPa, greater than or equal to 130 MPa, greater than or equal to 140 MPa, greater than or equal to 150 MPa, or higher. In an embodiment, the maximum CT of the glass substrate 110 may be greater than or equal to 20 MPa to less than or equal to 160 MPa, such as greater than or equal to 30 MPa to less than or equal to 160 MPa, greater than or equal to 40 MPa to less than or equal to 160 MPa, greater than or equal to 50 MPa to less than or equal to 160 MPa, greater than or equal to 60 MPa to less than or equal to 160 MPa, greater than or equal to 70 MPa to less than or equal to 160 MPa, greater than or equal to 80 MPa to less than or equal to 160 MPa, greater than or equal to 90 MPa to less than or equal to 160 MPa, greater than or equal to 100 MPa to less than or equal to 150 MPa, greater than or equal to 110 MPa to less than or equal to 140 MPa, greater than or equal to 120 MPa to less than or equal to 130 MPa, and all ranges and sub-ranges between the foregoing values.

[0160] The high fracture toughness values ​​of the glass compositions described herein can also achieve improved performance. The brittle limit of the glass substrate 110 produced using the glass compositions described herein depends at least in part on the fracture toughness. For this reason, the high fracture toughness of the glass compositions described herein allows a large amount of stored strain energy to be imparted to the glass substrate 110 formed therefrom without the glass substrate becoming brittle. The increased amount of stored strain energy that can then be included in the glass substrate 110 allows the glass substrate 110 to exhibit increased fracture resistance, which can be observed by the drop performance of the glass substrate 110. The relationship between the brittle limit and fracture toughness is described in U.S. Patent Application Publication No. 2020 / 0079689A1, entitled “Glass-based Articles with Improved Fracture Resistance,” published on March 12, 2020, the entire contents of which are incorporated herein by reference. The relationship between fracture toughness and drop performance is described in U.S. Patent Application Publication No. 2019 / 0369672 A1, entitled “Glass with Improved Drop Performance,” published on December 5, 2019, which is incorporated herein by reference in its entirety.

[0161] As mentioned above, DOC is measured using a scattered light polariscope (SCALP) technique known in the art. In some embodiments, DOC is provided as a fraction of the thickness (t) of the glass substrate 110. In embodiments, the depth of compression (DOC) of the glass substrate 110 may be greater than or equal to 0.15t to less than or equal to 0.25t, such as greater than or equal to 0.16t, greater than or equal to 0.17t, greater than or equal to 0.18t, greater than or equal to 0.19t, greater than or equal to 0.20t, greater than or equal to 0.21t to less than or equal to 0.24t, or greater than or equal to 0.22t to less than or equal to 0.23t, and all ranges and sub-ranges therebetween. The high DOC values ​​produced by the glass compositions described herein when ion-exchanged provide improved fracture resistance, particularly for situations where deep defects may be caused. For example, the deep DOC provides improved fracture resistance when dropped on a rough surface.

[0162] The thickness (t) of the glass substrate 110 is measured between the first major surface 112 and the first major surface 114. In an embodiment, the thickness of the glass substrate 110 may be in a range from greater than or equal to 0.1 mm to less than or equal to 4 mm, such as greater than or equal to 0.2 mm to less than or equal to 3.5 mm, greater than or equal to 0.3 mm to less than or equal to 3 mm, greater than or equal to 0.4 mm to less than or equal to 2.5 mm, greater than or equal to 0.5 mm to less than or equal to 2 mm, greater than or equal to 0.6 mm to less than or equal to 1.5 mm, greater than or equal to 0.7 mm to less than or equal to 1 mm, greater than or equal to 0.2 mm to less than or equal to 2 mm, and all ranges and sub-ranges therebetween.

[0163] A compressive stress layer can be formed in the glass by exposing the glass to an ion exchange medium. In an embodiment, the ion exchange medium can be a molten nitrate. In an embodiment, the ion exchange medium can be a molten salt bath and can include KNO3, NaNO3, or a combination thereof. In an embodiment, other sodium and potassium salts can be used in the ion exchange medium, such as, for example, sodium or potassium nitrite, sodium or potassium phosphate, or sodium or potassium sulfate. In an embodiment, the ion exchange medium can include a lithium salt, such as LiNO3. The ion exchange medium can further include additives that are typically included when ion exchanging glass, such as silicic acid. An ion exchange process is applied to the glass substrate 110 to form the glass substrate 110 including a compressive stress layer extending from the surface of the glass substrate 110 to a compression depth and a central tension region. The glass substrate 110 used for the ion exchange process can include any of the glass compositions described herein.

[0164] In an embodiment, the ion exchange medium comprises NaNO3. The sodium in the ion exchange medium is exchanged with lithium ions in the glass to generate compressive stress. In an embodiment, the ion exchange medium may include NaNO3 in an amount less than or equal to 95 wt%, such as less than or equal to 90 wt%, less than or equal to 80 wt%, less than or equal to 70 wt%, less than or equal to 60 wt%, less than or equal to 50 wt%, less than or equal to 40 wt%, less than or equal to 30 wt%, less than or equal to 20 wt%, less than or equal to 10 wt%, or less. In an embodiment, the ion exchange medium may include NaNO3 in an amount greater than or equal to 5 wt%, such as greater than or equal to 10 wt%, greater than or equal to 20 wt%, greater than or equal to 30 wt%, greater than or equal to 40 wt%, greater than or equal to 50 wt%, greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, greater than or equal to 90 wt%, or more. In embodiments, the ion exchange medium may include NaNO in an amount from greater than or equal to 0 wt % to less than or equal to 100 wt %, such as greater than or equal to 10 wt % to less than or equal to 90 wt %, greater than or equal to 20 wt % to less than or equal to 80 wt %, greater than or equal to 30 wt % to less than or equal to 70 wt %, greater than or equal to 40 wt % to less than or equal to 60 wt %, greater than or equal to 50 wt % to less than or equal to 90 wt %, and all ranges and subranges therebetween. In embodiments, the molten ion exchange medium includes 100 wt % NaNO .

[0165] In an embodiment, the ion exchange medium comprises KNO 3. In an embodiment, the ion exchange medium may include KNO 3 in an amount less than or equal to 95 wt %, such as less than or equal to 90 wt %, less than or equal to 80 wt %, less than or equal to 70 wt %, less than or equal to 60 wt %, less than or equal to 50 wt %, less than or equal to 40 wt %, less than or equal to 30 wt %, less than or equal to 20 wt %, less than or equal to 10 wt %, or less. In an embodiment, the ion exchange medium may include KNO 3 in an amount greater than or equal to 5 wt %, such as greater than or equal to 10 wt %, greater than or equal to 20 wt %, greater than or equal to 30 wt %, greater than or equal to 40 wt %, greater than or equal to 50 wt %, greater than or equal to 60 wt %, greater than or equal to 70 wt %, greater than or equal to 80 wt %, greater than or equal to 90 wt %, or more. In an embodiment, the ion exchange medium may include KNO in an amount from greater than or equal to 0 wt % to less than or equal to 100 wt %, such as greater than or equal to 10 wt % to less than or equal to 90 wt %, greater than or equal to 20 wt % to less than or equal to 80 wt %, greater than or equal to 30 wt % to less than or equal to 70 wt %, greater than or equal to 40 wt % to less than or equal to 60 wt %, greater than or equal to 50 wt % to less than or equal to 90 wt %, and all ranges and sub-ranges therebetween. In an embodiment, the molten ion exchange medium includes 100 wt % KNO .

[0166] The ion exchange medium may include a mixture of sodium and potassium. In an embodiment, the ion exchange medium is a mixture of potassium and sodium, such as a molten salt bath comprising NaNO3 and KNO3. In an embodiment, the ion exchange medium may include any combination of NaNO3 and KNO3 in the amounts described above, such as a molten salt bath containing 80 wt% NaNO3 and 20 wt% KNO3.

[0167] The glass composition can be exposed to the ion exchange medium by immersing a glass substrate made from the glass composition in a bath of the ion exchange medium, spraying the ion exchange medium onto a glass substrate made from the glass composition, or otherwise physically applying the ion exchange medium to a glass substrate made from the glass composition to form an ion-exchanged glass substrate. According to an embodiment, after exposure to the glass composition, the temperature of the ion exchange medium may be greater than or equal to 360° C. to less than or equal to 500° C., such as greater than or equal to 370° C. to less than or equal to 490° C., greater than or equal to 380° C. to less than or equal to 480° C., greater than or equal to 390° C. to less than or equal to 470° C., greater than or equal to 400° C. to less than or equal to 460° C., greater than or equal to 410° C. to less than or equal to 450° C., greater than or equal to 420° C. to less than or equal to 440° C., greater than or equal to 430° C. to less than or equal to 470° C., greater than or equal to 400° C. to less than or equal to 470° C., greater than or equal to 380° C. to less than or equal to 470° C., and all ranges and sub-ranges therebetween. In embodiments, the glass composition may be exposed to the ion exchange medium for a duration of greater than or equal to 10 minutes to less than or equal to 48 hours, such as greater than or equal to 10 minutes to less than or equal to 24 hours, greater than or equal to 0.5 hours to less than or equal to 24 hours, greater than or equal to 1 hour to less than or equal to 18 hours, greater than or equal to 2 hours to less than or equal to 12 hours, greater than or equal to 4 hours to less than or equal to 8 hours, and all ranges and sub-ranges therebetween.

[0168] The ion exchange process may include a second ion exchange treatment. In an embodiment, the second ion exchange treatment may include ion exchanging the glass substrate 110 in a second molten salt bath. The second ion exchange treatment may utilize any ion exchange medium described herein. In an embodiment, the second ion exchange treatment utilizes a second molten salt bath comprising KNO 3 .

[0169] The ion exchange process can be performed in an ion exchange medium under processing conditions that provide an improved compressive stress profile, such as disclosed in U.S. Patent Application Publication No. 2016 / 0102011, which is incorporated herein by reference in its entirety. In some embodiments, the ion exchange process can be selected to form a parabolic stress profile in the glass substrate 110, such as those described in U.S. Patent Application Publication No. 2016 / 0102014, which is incorporated herein by reference in its entirety.

[0170] After the ion exchange process is performed, it is understood that the composition at the surface of the ion-exchanged glass substrate 110 is different from the composition of the as-formed glass substrate (i.e., the glass substrate before the ion exchange process). This is due to the presence of one type of alkali metal ion (such as, for example, Li+ Or Na + ) are respectively replaced by larger alkali metal ions (such as, for example, Na + or K + ) replacement. However, in embodiments, the glass composition at or near the depth center of the glass substrate 110 will still have the composition of the as-formed non-ion-exchanged glass substrate used to form the glass substrate 110. As used herein, the center of the glass substrate 110 refers to any location in the glass substrate 110 that is at least 0.5t from each surface thereof, where t is the thickness of the glass substrate 110.

[0171] The coated articles disclosed herein can be incorporated into another article, such as an article with a display (or display article) (e.g., consumer electronic devices, including cell phones, tablets, computers, navigation systems, etc.), an architectural article, a transportation article (e.g., a car, train, airplane, marine vessel, etc.), an electrical article, or any article requiring a certain degree of transparency, scratch resistance, abrasion resistance, or a combination thereof. Exemplary articles incorporating any of the coated articles disclosed herein are shown in FIG. Figure 10A and 10B middle. Specifically, Figure 10A and 10B A consumer electronic device 200 is shown, comprising: a housing 202 having a front surface 204, a rear surface 206, and side surfaces 208; electrical components (not shown) at least partially or completely within the housing and including at least a controller, a memory, and a display 210 located at or adjacent to the front surface of the housing; and a cover substrate 212 located at or above the front surface of the housing such that it is located above the display. In some embodiments, at least one of the cover substrate 212 or a portion of the housing 202 may comprise any of the coated articles disclosed herein.

[0172] The drop test method involves performing a face drop test on a test block with the glass article attached. 61385 double-sided tape is attached to the test block to secure the glass article to the test block during the drop test described below. The thickness of the glass article to be tested is similar to or equal to the thickness that would be used in a given handheld consumer electronic device, such as 0.5 mm or 0.6 mm. A test block refers to a structure that is intended to mimic the size, shape, and weight distribution of a given device (such as a cellular phone). Hereinafter, the term "test block" refers to a structure that weighs 200 grams, is 133 mm long, 68 mm wide, and 9.4 mm high. In an embodiment, the test block has a size and weight similar to that of a handheld electronic device.

[0173] An exemplary apparatus that can be used to perform the drop test method is a drop machine such as Figure 11The apparatus dropper 10 is shown as reference numeral 10 in FIG. The apparatus dropper 10 includes a chuck 12 having chuck jaws 14. A test block 16 is placed in the chuck jaws 14 with the glassware attached to the chuck jaws and facing downward. The chuck 12 is ready to be dropped from, for example, an electromagnetic chuck lifter. Figure 12 , the chuck 12 is released, and during its fall, the chuck jaws 14 are triggered to open by, for example, a proximity sensor. When the chuck jaws 14 open, the test block 16 is released. Figure 13 , the falling test piece 16 hits the falling surface 18. The falling surface 18 can be sandpaper positioned on a steel plate, for example, No. 180 sandpaper. If the glass product attached to the test piece withstands the drop (that is, does not break), then the chuck 12 is set at a higher height and the test is repeated. Thus, the failure height is the lowest height at which the test piece including the glass product falls and the glass composition fails. At multiple heights, such as 22 cm, 30 cm, 40 cm, 50 cm, 60 cm, and at a height of 10 cm increments, a single glass product is tested until the glass product fails by showing damage. The sandpaper is replaced after the glass fails. Unless otherwise indicated, No. 80 sandpaper is used herein.

[0174] In one or more embodiments, the coated glass article may have a failure height of 50 cm or greater, such as 75 cm or greater, 100 cm or greater, 125 cm or greater, 150 cm or greater, 175 cm or greater, or even 200 cm or greater. In some embodiments, the coated glass article has a failure height of about 50 cm to about 220 cm, such as about 50 cm to about 200 cm, about 50 cm to about 150 cm, about 50 cm to about 100 cm, about 100 cm to about 220 cm, about 100 cm to about 200 cm, about 100 cm to about 150 cm, about 150 cm to about 220 cm, about 150 cm to about 200 cm, about 200 cm to about 220 cm, or any combination of these ranges.

[0175] As used herein, the term "retained strength" refers to the strength of a coated glass article after it is damaged by an impact force when the article is bent to impart tensile stress. The damage is caused according to the method described in U.S. Patent Publication No. 2019 / 0072469A1, which is incorporated herein by reference. For example, an apparatus for impact testing a glass article such as Figure 141100. Apparatus 1100 includes a pendulum 1102 comprising a bob 1104 attached to a pivot 1106. As used herein, the term "bob" in reference to a pendulum is a weight suspended from and connected to a pivot by an arm. Thus, bob 1104 is shown connected to pivot 1106 by arm 1108. Bob 1104 comprises a base 1110 for receiving a glass article, and the glass article is secured to the base. Apparatus 1100 further comprises an impact object 1140 positioned such that when bob 1104 is released from a position at an angle greater than zero relative to a balanced position, a surface of bob 1104 contacts impact object 1140. The impact object comprises an abrasive sheet having an abrasive surface to be placed in contact with an outer surface of the glass article. The abrasive sheet may comprise sandpaper having a grit range of 30 to 400, or 100 to 300, such as 180.

[0176] For the purposes of this disclosure, the impact object takes the form of a 6 mm diameter 180 grit sandpaper disc affixed to the apparatus. A glass article having a thickness of approximately 600.0 μm is affixed to the bob. A new sandpaper disc is used for each impact. Damage to the glass article is inflicted by swinging the apparatus's arm to an angle of approximately 90°.

[0177] After twelve hours or more of inflicting damage, the glass article breaks in a four-point bend (4PB) test as defined by ASTM C-158. The damaged glass article is placed on a support rod (support span) with the damaged portion located on the bottom (i.e., on the tension side) and between the loading path (loading span). For the purposes of this disclosure, the loading span is 15 mm and the support span is 30 mm. A screw-driven testing machine ( The loading was carried out at a constant displacement rate of 5 mm / min in a Norwood, Massachusetts, USA until the glass failed.

[0178] The applied fracture stress (or applied failure stress) in four-point bending (4PB) is calculated by the following equation (4):

[0179]

[0180] Where P is the maximum failure load, L (=30 mm) is the distance between the support rods (support span), a (=15 mm) is the distance between the loading rods (loading span), b is the width of the glass sheet, and h is the thickness of the glass sheet. In four-point bending, the stress is constant across the loading span, and therefore the damaged area is subjected to Mode I uniaxial tensile stress loading. The retained strength of a glass article is the highest applied fracture stress at which failure does not occur.

[0181] In one or more embodiments, the coated glass article has a retained strength greater than or equal to 250 MPa, such as greater than or equal to 300 MPa, greater than or equal to 350 MPa, or even greater than or equal to 400 MPa. In some embodiments, the coated glass article has a retained strength of about 250 MPa to about 400 MPa, such as about 250 MPa to about 350 MPa, about 250 MPa to about 300 MPa, about 300 MPa to about 400 MPa, about 300 MPa to about 350 MPa, about 350 MPa to about 400 MPa, or any combination of these ranges.

[0182] Example

[0183] The embodiments will be further illustrated by the following examples. It should be understood that these examples are not limited to the above embodiments.

[0184] Example 1

[0185] In this example, the coated glass articles and uncoated control glass articles (referred to as "Sample 1," "Sample 2," "Comparative Example 1," and "Comparative Example 2," respectively) were tested using the drop test method described in detail herein. Sample 1 and Comparative Example 1 used Incorporated production Glass Sheets having the compositions specified in Table 1 below. Sample 2 and Comparative Example 2 used glass sheets having the compositions shown in Table 2 below. Table 3 shows suitable exemplary compositions containing the composition ranges for the glass sheets associated with Tables 1 and 2.

[0186] Table 1 - Substrate composition of Comparative Example 1 and Sample 1

[0187] composition Mol% <![CDATA[SiO2]]> 58.65 <![CDATA[Al2O3]]> 17.85 <![CDATA[P2O5]]> 1.47 <![CDATA[B2O3]]> 4.22 MgO 1.19 <![CDATA[Li2O]]> 7.70 <![CDATA[Na2O]]> 8.72 <![CDATA[K2O]]> 0.07 <![CDATA[TiO2]]> 0.10 <![CDATA[SnO2]]> 0.04

[0188] Table 2 - Substrate composition of Comparative Example 2 and Sample 2

[0189]

[0190]

[0191] Table 3 - Suitable substrate compositions

[0192] composition Mol% <![CDATA[SiO2]]> 50.0-70.0 <![CDATA[Al2O3]]> 10.0-20.0 <![CDATA[P2O5]]> 0.0-2.0 <![CDATA[B2O3]]> 1.0-6.0 <![CDATA[Li2O]]> 5.0-10.0 <![CDATA[Na2O]]> 1.0-10.0 <![CDATA[K2O]]> 0.01-1.0

[0193] As mentioned above, each of Comparative Examples 1 and 2 and Samples 1 and 2 employed substrates having glass compositions within the ranges shown in Table 3. It is believed that similar glasses having compositions within the ranges of Table 3 will have similarly improved drop performance and retained strength when coated with the optical coatings of the present disclosure. Furthermore, without being bound by theory, it is believed that other glass compositions outside the ranges of Table 3 but incorporating further aspects of the present disclosure (e.g., glass compositions having a Li2O:Na2O ratio of 1.2 to 2.0 and / or being substantially free of Ta2O5, HfO2, La2O3, and Y2O3) will also have similarly improved drop performance and retained strength when coated with the optical coatings of the present disclosure.

[0194] Samples 1 and 2 were formed by coating Comparative Example 1 and Comparative Example 2, respectively, with the coatings shown in Table 4, wherein Layer 1 is the layer disposed on the substrate and Layer 19 is the outermost layer of the coating. Tables 5-9 show other suitable exemplary coatings, and it is believed that articles having these coatings have the same or similar drop performance and retained strength improvements as the disclosed glass substrates. The coatings of Tables 5-9 (with Layer 1 disposed on (or in contact with) the substrate in each design) are exemplary additional coatings that, when coated on the substrates of Tables 1-3, are also believed to have the same or similar drop performance and retained strength improvements as the disclosed glass substrates and the coatings of this example using the coatings in Table 4.

[0195] Table 4 - Optical coating design

[0196] layer Material Layer thickness (nm) 1 SiO2 25 2 SiOxNy 10 3 SiO2 69.2 4 SiOxNy 21.4 5 SiO2 57.9 6 SiOxNy 35.5 7 SiO2 38.3 8 SiOxNy 50.5 9 SiO2 19.6 10 SiOxNy 62.6 11 SiO2 6.4 12 SiOxNy 2050 13 SiO2 8 14 SiNx 42.5 15 SiO2 25.75 16 SiNx 40.5 17 SiO2 47.2 18 SiNx 22.1 19 SiO2 133.0

[0197] Table 5 - Optical coating design

[0198]

[0199]

[0200] Table 6 - Optical coating design

[0201]

[0202]

[0203] Table 7 - Optical coating design

[0204]

[0205]

[0206] Table 8 - Optical coating design

[0207] layer Material Layer thickness (nm) 1 SiO2 20 2 SiOxNy 11.5 3 SiO2 69.1 4 SiOxNy 25.21 5 SiO2 58.96 6 SiOxNy 40.59 7 SiO2 39.78 8 SiOxNy 56.56 9 SiO2 20.82 10 SiOxNy 69.27 11 SiO2 6.8 12 SiOxNy 1960 13 SiO2 9.34 14 SiOxNy 58.47 15 SiO2 33.71 16 SiOxNy 32.05 17 SiO2 125.16

[0208] Table 9 - Optical coating design

[0209]

[0210]

[0211] As described above, the coated articles of the present disclosure were tested using a drop test method. Drop testing was conducted using a "test block" designed to simulate a mobile handheld device being dropped from a specific height (22 cm to 220 cm) and a specific angle (0 degrees, 30 degrees, etc.) onto a desired drop surface (sandpaper of a specific grit size (30, 80, 180), coarse sandpaper grit of various materials (e.g., Al2O3, garnet), rough granite, asphalt, etc.). The drop tests were conducted using a commercial drop tower manufactured by Shinyei Corporation (however, machines with similar functionality from different manufacturers may be used). An example drop tower is shown at Figure 19 The drop tower has a drop platform (A), a drop surface (B), a stop buffer (C), a chuck assembly (D) and an electromagnetic chuck lifter I, a chuck lift winch (F), a guide rod (G), and a main control panel (H).

[0212] The cover glass to be tested is assembled in a test block designed to simulate a mobile handheld device. A cross section of the test block is shown in Figure 20 middle. Figure 21 Displays a detailed view of the test block. Figure 22 Schematic diagram showing the back of the test block. Figure 23 An example of a cover glass in an assembled test block is shown. The properties of the test block are shown in Table 10.

[0213] Table 10 - Test blocks for drop tests

[0214] characteristic Test Block Mass (g) 200 Glass size X / Y (mm) 130.2×65.2 Mass / unit area (g / mm^2) 0.02355979 Frame protrusion (mm) 0.05

[0215] For a controlled and repeatable drop test, perform the drop at a specific angle and onto specific sandpaper that simulates a real-life surface. Drop the test piece horizontally (zero degrees) onto 3M 80 grit sandpaper. For a flat drop onto 3M 80 grit Garnet sandpaper, first Figure 24The drop surface is prepared as shown. Two layers of sandpaper are used, the bottom sandpaper "A" is 180 Al2O3 paper acting as a substrate, and the desired test surface "B", here 80 3M garnet sandpaper "B", is placed on top of "A". The bottom piece (A) remains in place after each drop and is used only as a means to prevent the top piece from moving from its placement position. The top piece (B) is replaced each time a new device is loaded (i.e., one piece of sandpaper is used for each device tested). Magnets are placed at the corners of the sandpaper to increase stability. This keeps the sandpaper fixed in place during the drop procedure and there is no displacement. Make sure the sandpaper is level and there is no visible damage in the target center area where the test block device will fall. For the flat drop test, a dual-axis inclinometer is used to align the assembled test block with cover glass in the claws of the drop tower to be horizontal, and make sure the angle is aligned to zero degrees.

[0216] The drop test was performed at a starting height of 22 cm, then at heights of 30 cm, 40 cm, etc., with increments of 10 cm. The chuck was raised to the desired drop height (starting at 22 cm) and dropped horizontally onto the drop surface. High-speed video was captured from the X and Y directions to ensure that the drop was horizontal and <2 degrees in both directions (i.e., along the minor and major axes of the test block). After falling from the desired height, the cover glass was inspected for cracks and fractures. If there was a crack or fracture in the glass, it was considered a failure and the failure height was recorded; and if there was no crack or fracture in the cover glass, the device was raised to the next height and dropped, continuing this process until the cover glass was cracked or fractured. Once the cover glass failed, the sandpaper was removed and new sandpaper was placed according to the above procedure, and a new cover glass test block was loaded and adjusted to a level. The starting height was brought to 22 cm and continued from there.

[0217] The same drop procedure was followed for the comparative and coated samples. For each condition, each cover glass sample was dropped 15-20 times and the corresponding failure heights were recorded. The resulting data is an overview of the product description and the corresponding failure heights. The data was plotted as a single value plot ( Figure 15 and 16 ) and compared the average failure results of the control and coated parts. After the drop, the samples were subjected to failure mode analysis (FMA) to understand the nature of the failure.

[0218] The results of the drop test method are shown in Figure 15 and Figure 16 In. Figure 15 and 16 As shown, the coated samples (e.g., samples 1 and 2, Figure 15 and 16 ) compared to the uncoated glass substrates of Comparative Examples 1 and 2 (designated as "S1" and "S2" in Figure 15 and16 ) have improved drop performance, indicating that the combination of the coating and the glass improves the drop performance of the entire glass article. Glass and the compositions of Tables 1-2), the drop range proposed for Comparative Examples 1 and 2 is 22 cm to 175 cm, and for the coated glass (ie, Samples 1 and 2), the range is 50 cm to 220 cm.

[0219] Example 2

[0220] In Example 2, Samples 1 and 2 and Comparative Examples 1 and 2 were tested for retained strength after damage by an impact force using the method described above and now described in further detail.

[0221] In the retained strength test, controlled damage is caused on the surface of the test cover glass sample and the retained strength (MPa) of the test sample is measured using the four-point bend test (4PB) specified by ASTM (C-158) after damage. The 4PB will provide the failure stress after damage. The uncoated comparative example and the coated sample are tested similarly and compared. For sharp contact damage, the coated sample is significantly better than the uncoated comparative example. It is believed that the coating prevents damage from being caused on the surface compared to the uncoated comparative example. Damage is caused on the surface using 180 grit garnet sandpaper. A schematic diagram of the impact damage equipment is shown in Figure 14 as well as Figure 25 A-25C.

[0222] To create defects on the surface, use a hole punch to cut the required sandpaper (180 grit garnet). The diameter of the hole is about 5 mm. Fix this circular cut 180 grit sandpaper with double-sided tape on the surface of the Figure 26 To ensure safe collection of the broken specimen after testing, the test cover glass was first laminated on one side with 130 μm thick vinyl tape, covering the entire surface. The laminated cover glass was then placed on the flat surface of a sample holder with the non-laminated surface facing outward and clamped with screws. Figure 27 Shows the preparation of the cover glass sample used to create the defects. Figure 28 Shows a cover glass sample mounted on an impact damage device. The sample holder is typically made of Made of material.

[0223] The impact angle (θ) is adjustable and is adjusted to the desired angle and released manually. The impact angle tested is 90 degrees. After the damage is caused, the failure stress (MPa) is measured using the four-point bending test method defined by ASTM C-158. The four-point test apparatus is shown in Figure 29The device has a pair of supporting blades and a pair of loading blades. This device is fixed to an Instron testing machine or similar equipment. Four-point bending is usually used to measure the edge strength of parts, however, it is used here to understand the impact of damage. If the damage is severe enough, failure will occur at the damaged part rather than the edge. This is believed to be because the strength caused by the damage is lower than the edge strength (glass fails at the weakest link under tension), resulting in a weakening of the strength of the glass at the damaged part.

[0224] After the damage is caused to the test cover glass by the slapper, the damaged side of the test sample is placed under tension (facing downward) at the center of the support rod of the 4PB device, and the force is applied vertically by the loading rod until the test sample breaks. The load / support span is selected so that the load-deflection curve is linear. This will enable us to use the linear conversion equation from failure load (kgf) to fracture stress (MPa), as shown in the following equation (5):

[0225]

[0226] In the load-stress conversion equation shown in equation (5), P is the maximum failure load, L (=30 mm) is the distance between the support rods (support span), a (=15 mm) is the distance between the loading rods (loading span), b is the width of the glass sheet, and h is the thickness of the glass sheet. For a 0.6 mm thick specimen and linear load-deflection curve, the span ratio is 15 mm / 30 mm (i.e., the loading span spacing is 15 mm and the support span spacing is 30 mm).

[0227] like Figure 30 As shown, the defective cover glass was placed on the support blades in the 4PB apparatus with the damaged part centered between the support blades and facing downward (the damaged part was in tension and facing downward). The results of the retained strength test are shown in Figure 17 and Figure 18 In the two figures, the failure stress (MPa) of each test specimen is reported. Figure 17 and 18 As shown, the coated samples (i.e., samples 1 and 2, Figure 17 and 18 ) compared to uncoated glass (i.e., Comparative Examples 1 and 2, Figure 17 and 18 CE1 and CE2), showed improved retained strength after damage by impact.

[0228] It should be understood that the various disclosed embodiments may relate to specific features or elements described in conjunction with the specific embodiment. It should also be understood that although specific features or elements are described with respect to a specific embodiment, they may be interchanged or combined with alternative embodiments in various combinations or permutations not shown.

[0229] As described herein, a first aspect of the present disclosure is a coated glass article that may include a glass substrate comprising a first major surface and a second major surface. The first major surface and the second major surface may be opposite sides of the glass substrate. The composition of the glass substrate may include: SiO2 in an amount greater than or equal to 50.0 mol% and less than or equal to 70.0 mol%; Al2O3 in an amount greater than or equal to 10.0 mol% and less than or equal to 20.0 mol%; P2O5 in an amount greater than or equal to 0.0 mol% and less than or equal to 2.0 mol%; B2O3 in an amount greater than or equal to 1.0 mol% and less than or equal to 6.0 mol%; Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 10.0 mol%; and K2O in an amount greater than or equal to 0.01 mol% and less than or equal to 1.0 mol%. The coated glass article may further comprise an optical coating disposed on the first major surface of the glass substrate. The optical coating may form an antireflective surface. The optical coating may comprise a scratch-resistant layer and an antireflective coating comprising a plurality of alternating high and low refractive index layers disposed between the scratch-resistant layer and the glass substrate. The optical coating may have a physical thickness of from about 50 nm to about 10 microns. The coated glass article may exhibit a maximum hardness of from about 10 GPa to about 30 GPa measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, as measured by a Bosch indenter hardness test. The coated glass article may exhibit a retained strength of greater than or equal to 250 MPa.

[0230] According to a second aspect of the present disclosure, the first aspect is provided, wherein the coated glass article exhibits a retained strength of about 250 MPa to about 400 MPa.

[0231] According to a third aspect of the present disclosure, there is provided any of the preceding aspects, wherein the coated glass article has a failure height greater than or equal to 50 cm as measured on 80 grit sandpaper according to the drop test method.

[0232] According to a fourth aspect of the present disclosure, there is provided any of the preceding aspects, wherein the coated glass article has a failure height of about 50 cm to about 220 cm as measured on 80 grit sandpaper according to the drop test method.

[0233] According to a fifth aspect of the present disclosure, there is provided any of the aforementioned aspects, wherein the compressive stress of the glass substrate is greater than or equal to 500 MPa.

[0234] According to a sixth aspect of the present disclosure, there is provided any one of the aforementioned aspects, wherein the maximum central tension of the glass substrate is greater than or equal to 20 MPa.

[0235] According to a seventh aspect of the present disclosure, there is provided any one of the aforementioned aspects, wherein the maximum central tension of the glass substrate is less than or equal to 160 MPa.

[0236] According to an eighth aspect of the present disclosure, there is provided any of the preceding aspects, wherein the glass substrate has a depth of layer greater than or equal to 3.0 micrometers.

[0237] According to a ninth aspect of the present disclosure, there is provided any of the preceding aspects, wherein the glass substrate has a depth of layer less than or equal to 12 micrometers.

[0238] According to a tenth aspect of the present disclosure, there is provided any of the preceding aspects, wherein the plurality of alternating high and low refractive index layers comprises at least 3 layers.

[0239] According to an eleventh aspect of the present disclosure, there is provided any of the aforementioned aspects, wherein each low refractive index layer comprises a silicon-containing oxide, and each high refractive index layer comprises a silicon-containing nitride or a silicon-containing oxynitride.

[0240] According to a twelfth aspect of the present disclosure, there is provided any one of the preceding aspects, wherein the scratch-resistant layer is a high refractive index layer.

[0241] According to a thirteenth aspect of the present disclosure, there is provided any of the preceding aspects, wherein the scratch-resistant layer has a thickness of about 200 nm to about 5000 nm.

[0242] According to a fourteenth aspect of the present disclosure, there is provided any of the aforementioned aspects, wherein each low refractive index layer comprises SiO2, Al2O3, GeO2, SiO, AlO x N y 、SiO x N y 、Si u Al v O x N y , MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3 and CeF3, and each high refractive index layer contains Si u Al v O x N y, Ta2O5, Nb2O5, AlN, Si3N4, AlO x N y 、SiO x N y 、SiN x 、SiN x H y , at least one of HfO2, TiO2, ZrO2, Y2O3, Al2O3 and MoO3.

[0243] According to a fifteenth aspect of the present disclosure, any of the preceding aspects is provided, wherein the coated glass article exhibits a double-sided average light transmittance greater than or equal to about 92% measured at the antireflective surface within a light wavelength region ranging from about 400 nm to about 800 nm.

[0244] According to a sixteenth aspect of the present disclosure, there is provided any of the preceding aspects, wherein the coated glass article exhibits an average single-sided reflectivity of less than or equal to 3% over a wavelength range of light from about 410 nm to about 1050 nm.

[0245] According to a seventeenth aspect of the present disclosure, any of the preceding aspects is provided, wherein the coated glass article exhibits either or both of the following: under an International Commission on Illumination illuminant at normal incidence, the article's transmission color coordinates in the (L*, a*, b*) colorimetric system exhibit a reference point color shift of less than about 2 measured at the antireflective surface relative to a reference point, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmission color coordinates of the substrate; and under an International Commission on Illumination illuminant at normal incidence, the article's reflection color coordinates in the (L*, a*, b*) colorimetric system exhibit a reference point color shift of less than about 5 measured at the antireflective surface relative to a reference point, the reference point comprising at least one of the color coordinates (a*=0, b*=0), the color coordinates (a*=-2, b*=-2), and the reflection color coordinates of the substrate. When the reference point is the color coordinates (a*=0, b*=0), the color shift is given by √((a*=0, b*=0)) / √(a*=0) / √(a*=0) / √(b ...a*=0) / √(b*=0) / √(a*=0) / √(b*=0) / √(a*=0) / √(a*=0) / √(b*=0) / √ 制品 ) 2 +(b* 制品 ) 2 ) is defined. When the reference point is the color coordinate (a*=-2, b*=-2), the color shift is given by √((a* 制品 +2) 2 +(b* 制品 +2) 2 ). When the reference point is the color coordinate of the substrate, the color shift is defined by √((a* 制品 -a* 基板 )2 +(b* 制品 -b* 基板 ) 2 )definition.

[0246] According to an eighteenth aspect of the present disclosure, there is provided a first aspect, wherein the coated glass article exhibits a single-sided average photopic reflectance of about 10% or less measured at the anti-reflective surface at near-normal incidence over a wavelength range of about 400 nm to about 700 nm; and the article reflectance color coordinates in the (L*, a*, b*) colorimetric system under an International Commission on Illumination illuminant for at least one incident angle of 0 to 90 degrees exhibit a reference point color shift of greater than about 18 measured at the anti-reflective surface relative to a reference point, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflectance color coordinates of the substrate. When the reference point is the color coordinates (a*=0, b*=0), the color shift is given by √((a*=0, b*=0)) / √(a*=0) / √(b*=0 ... 制品 ) 2 +(b* 制品 ) 2 ). When the reference point is the color coordinate of the substrate, the color shift is defined by √((a* 制品 -a* 基板 ) 2 +(b* 制品 -b* 基板 ) 2 )definition.

[0247] According to a nineteenth aspect of the present disclosure, there is provided a first aspect, wherein the coated glass article exhibits either or both of the following: a one-sided photopic average light reflectance of about 12% or greater; and a one-sided maximum reflectance of about 12% or greater measured at the anti-reflective surface for at least one near-normal angle of incidence within a wavelength region of light ranging from about 400 nm to about 700 nm. The article exhibits, under an illuminator of the International Commission on Illumination, for at least one angle of incidence from 0 degrees to 90 degrees, an article reflectance color coordinate in the (L*, a*, b*) colorimetric system that exhibits a reference point color shift of greater than 12 measured at the anti-reflective surface relative to a reference point, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflectance color coordinates of the substrate. When the reference point is the color coordinates (a*=0, b*=0), the color shift is given by √((a*=0, b*=0)) / √(a*=0) / √(b*=0 ... 制品 ) 2 +(b* 制品 ) 2 ). When the reference point is the color coordinate of the substrate, the color shift is defined by √((a* 制品 -a* 基板 )2 +(b* 制品 -b* 基板 ) 2 )definition.

[0248] According to a twentieth aspect of the present disclosure, a coated glass article for a mobile display cover includes a glass substrate, the composition of the glass substrate including: SiO2 in an amount greater than or equal to 50.0 mol% and less than or equal to 70.0 mol%, Al2O3 in an amount greater than or equal to 10.0 mol% and less than or equal to 25.0 mol%, and Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 15.0 mol%, wherein the glass substrate includes a first major surface and a second major surface, wherein the first major surface and the second major surface are opposite sides of the glass substrate, and wherein the glass substrate includes: a layer depth greater than or equal to 3 μm, an elastic modulus greater than or equal to 72 GPa, and a strength greater than or equal to 0.7 MPa·m 0.5 and an optical coating disposed on the first major surface of the glass substrate, the coated glass article exhibiting: an average photopic transmittance greater than 85% and an average photopic reflectance less than 8%; a maximum hardness of about 12 GPa to about 30 GP measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, the maximum hardness being measured by a Bosch Indenter Hardness Test; and a retained strength greater than or equal to 250 MPa.

[0249] According to a twenty-first aspect of the present disclosure, the twentieth aspect is provided, wherein the coated glass article has a retained strength of about 250 MPa to about 400 MPa.

[0250] According to a twenty-second aspect of the present disclosure, there is provided the twentieth or twenty-first aspect, wherein the coated glass article has a failure height greater than or equal to 50 cm as measured on 80 grit sandpaper according to the drop test method.

[0251] According to a twenty-third aspect of the present disclosure, there is provided any one of aspects 20 to 22, wherein the coated glass article has a failure height of greater than or equal to 50 cm to less than or equal to 220 cm as measured on 80 grit sandpaper according to the drop test method.

[0252] According to the twenty-fourth aspect of the present disclosure, any one of the twentieth to twenty-third aspects is provided, wherein the composition of the glass substrate further comprises: P2O3 in an amount greater than or equal to 0.0 mol% and less than or equal to 5.0 mol%; B2O3 in an amount greater than or equal to 0.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 15.0 mol%; and K2O in an amount greater than or equal to 0.0 mol% and less than or equal to 1.0 mol%.

[0253] According to a twenty-fifth aspect of the present disclosure, there is provided any one of the twentieth to twenty-fourth aspects, wherein the scratch-resistant layer is a high refractive index layer.

[0254] According to a twenty-sixth aspect of the present disclosure, there is provided any one of the 20th to 25th aspects, wherein the maximum hardness is greater than or equal to 15 MPa and less than or equal to 30 MPa.

[0255] According to a twenty-seventh aspect of the present disclosure, there is provided any one of the 20th to 26th aspects, wherein the scratch-resistant layer has a thickness of about 200 nm to about 5000 nm.

[0256] According to a twenty-eighth aspect of the present disclosure, there is provided any one of aspects 20 to 27, wherein the optical coating forms an anti-reflective surface, the optical coating comprising an anti-reflective coating and a scratch-resistant layer, the anti-reflective coating comprising a plurality of alternating high refractive index layers and low refractive index layers; each low refractive index layer comprising SiO2, Al2O3, GeO2, SiO, AlO x N y 、SiO x N y 、Si u Al v O x N y , MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3 and CeF3, and each high refractive index layer contains Si u Al v O x N y , Ta2O5, Nb2O5, AlN, Si3N4, AlO x N y 、SiO x N y 、SiN x 、SiN x H y, at least one of HfO2, TiO2, ZrO2, Y2O3, Al2O3 and MoO3.

[0257] According to a twenty-ninth aspect of the present disclosure, there is provided any one of aspects 20 to 28, wherein the plurality of alternating high refractive index layers and low refractive index layers comprises at least 3 layers.

[0258] According to a thirtieth aspect of the present disclosure, there is provided any one of the twentieth to twenty-seventh aspects, wherein the optical coating comprises a composition gradient.

[0259] According to the thirty-first aspect of the present disclosure, there is provided any one of aspects 20 to 30, wherein the coated glass article exhibits a double-sided average light transmittance greater than or equal to about 92% measured at the anti-reflective surface in a light wavelength region ranging from about 400 nm to about 800 nm.

[0260] According to a thirty-second aspect of the present disclosure, there is provided any one of aspects 20 to 31, wherein the coated glass article exhibits either or both of the following: under an International Commission on Illumination illuminant at normal incidence, the article transmission color coordinates in the (L*, a*, b*) colorimetric system exhibit a reference point color shift of less than about 2 measured at the antireflective surface relative to a reference point, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmission color coordinates of the substrate; and under an International Commission on Illumination illuminant at normal incidence, the article reflection color coordinates in the (L*, a*, b*) colorimetric system exhibit a reference point color shift of less than about 5 measured at the antireflective surface relative to a reference point, the reference point comprising at least one of the color coordinates (a*=0, b*=0), the color coordinates (a*=-2, b*=-2), and the reflection color coordinates of the substrate. When the reference point is the color coordinates (a*=0, b*=0), the color shift is given by √((a*=0, b*=0)) / √(a*=0) / √(a*=0) / √(b ...a*=0) / √(b*=0) / √(a*=0) / √(b*=0) / √(a*=0 制品 ) 2 +(b* 制品 ) 2 ) is defined. When the reference point is the color coordinate (a*=-2, b*=-2), the color shift is given by √((a* 制品 +2) 2 +(b* 制品 +2) 2 ). When the reference point is the color coordinate of the substrate, the color shift is defined by √((a* 制品 -a* 基板 ) 2 +(b* 制品 -b*substrate) 2 )definition.

[0261] According to a thirty-third aspect of the present disclosure, there is provided any one of aspects 20 to 32, wherein the coated glass article exhibits an average single-sided reflectivity of less than or equal to 3% over a wavelength range of light from about 410 nm to about 1050 nm.

[0262] According to a thirty-fourth aspect of the present disclosure, there is provided any one of the 20th to 33rd aspects, wherein the compressive stress of the glass substrate is greater than or equal to 500 MPa.

[0263] According to a thirty-fifth aspect of the present disclosure, there is provided any one of the 20th to 34th aspects, wherein the maximum central tension of the glass substrate is greater than or equal to 20 MPa.

[0264] According to a thirty-sixth aspect of the present disclosure, there is provided any one of the 20th to 35th aspects, wherein the maximum central tension of the glass substrate is less than or equal to 160 MPa.

[0265] According to a thirty-seventh aspect of the present disclosure, a coated glass article comprises: a glass substrate comprising a first major surface and a second major surface, wherein the first major surface and the second major surface are opposite sides of the glass substrate; an optical coating disposed on the first major surface of the glass substrate, the optical coating forming an antireflective surface, wherein the optical coating comprises a scratch-resistant layer and an antireflective coating, the antireflective coating comprising a plurality of alternating high and low refractive index layers disposed between the scratch-resistant layer and the glass substrate; wherein the optical coating has a physical thickness of from about 50 nm to about 10 microns; wherein the coated glass article exhibits a maximum hardness of from about 10 GPa to about 30 GPa measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, the maximum hardness being measured by a Bosch Indenter Hardness Test; and wherein the coated glass article has a failure height of from about 50 cm to about 220 cm as measured on 80 grit garnet sandpaper according to a drop test method.

[0266] According to a thirty-eighth aspect of the present disclosure, the thirty-seventh aspect is provided, wherein the coated glass article exhibits a retained strength greater than or equal to 250 MPa.

[0267] According to a thirty-ninth aspect of the present disclosure, the thirty-seventh aspect is provided, wherein the coated glass article exhibits a retained strength of about 250 MPa to about 400 MPa.

[0268] According to a 40th aspect of the present disclosure, there is provided any one of aspects 37 to 39, wherein the glass substrate comprises a glass ceramic substrate.

[0269] According to the forty-first aspect of the present disclosure, a consumer electronic product comprises: a housing comprising a front surface, a rear surface, and side surfaces; electrical components at least partially located within the housing, the electrical components comprising a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a coated glass article positioned over the display, wherein the coated glass article is according to any one of aspects thirty-seven to fortieth and aspects forty-eight to fifty.

[0270] According to the forty-second aspect of the present disclosure, there is provided any one of the first to nineteenth aspects, wherein the composition of the glass substrate further comprises a molar ratio of lithium to sodium (Li2O:Na2O) of greater than or equal to 1.2 to less than or equal to 2.0.

[0271] According to a forty-third aspect of the present disclosure, there is provided any one of the first to nineteenth aspects, wherein the composition of the glass substrate is substantially free of or free of Ta2O5, HfO2, La2O3 and Y2O3.

[0272] According to the forty-fourth aspect of the present disclosure, any one of the first to nineteenth aspects is provided, wherein the composition of the glass substrate comprises: 61-67 mol% SiO2; 12-18 mol% Al2O3; 0.25-1.25 mol% P2O5; 2-4 mol% B2O3; 6-9 mol% Li2O; 3-6 mol% Na2O; and 0.1-0.5 mol% K2O.

[0273] According to a forty-fifth aspect of the present disclosure, there is provided any one of aspects 20 to 36, wherein the composition of the glass substrate further comprises: Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 10.0 mol%; and a molar ratio of lithium to sodium (Li2O:Na2O) greater than or equal to 1.2 and less than or equal to 2.0.

[0274] According to a forty-sixth aspect of the present disclosure, there is provided any one of aspects 20 to 36, wherein the composition of the glass substrate is substantially free of or free of Ta2O5, HfO2, La2O3, and Y2O3.

[0275] According to the forty-seventh aspect of the present disclosure, any one of the twentieth to thirty-sixth aspects is provided, wherein the composition of the glass substrate comprises: 61-67 mol% SiO2; 12-18 mol% Al2O3; 0.25-1.25 mol% P2O5; 2-4 mol% B2O3; 6-9 mol% Li2O; 3-6 mol% Na2O; and 0.1-0.5 mol% K2O.

[0276] According to a forty-eighth aspect of the present disclosure, there is provided any one of aspects thirty-seven to fortieth, wherein the composition of the glass substrate comprises: Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 10.0 mol%; and a molar ratio of lithium to sodium (Li2O:Na2O) greater than or equal to 1.2 and less than or equal to 2.0.

[0277] According to a forty-ninth aspect of the present disclosure, there is provided any one of aspects thirty-seven to fortieth, wherein the composition of the glass substrate is substantially free of or free of Ta2O5, HfO2, La2O3 and Y2O3.

[0278] According to the fiftieth aspect of the present disclosure, any one of aspects 37 to 40 is provided, wherein the composition of the glass substrate comprises: 61-67 mol% SiO2; 12-18 mol% Al2O3; 0.25-1.25 mol% P2O5; 2-4 mol% B2O3; 6-9 mol% Li2O; 3-6 mol% Na2O; and 0.1-0.5 mol% K2O.

[0279] According to aspect 51 of the present disclosure, a consumer electronic product comprises: a housing comprising a front surface, a rear surface, and side surfaces; electrical components at least partially within the housing, the electrical components comprising a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a coated glass article positioned over the display, wherein the coated glass article is according to any one of aspects 1 to 19 and 42 to 44.

[0280] According to aspect 52 of the present disclosure, a consumer electronic product comprises: a housing comprising a front surface, a rear surface, and side surfaces; electrical components at least partially within the housing, the electrical components comprising a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a coated glass article positioned over the display, wherein the coated glass article is according to any one of aspects 20 to 36 and 45 to 47.

Claims

1. A coated glass article comprising: A glass substrate comprising a first major surface and a second major surface, wherein the first major surface and the second major surface are opposite sides of the glass substrate, wherein the composition of the glass substrate comprises: SiO2 in an amount greater than or equal to 50.0 mol% and less than or equal to 70.0 mol%; Al2O3 in an amount greater than or equal to 10.0 mol% and less than or equal to 20.0 mol%; P2O5 in an amount greater than or equal to 0.0 mol% and less than or equal to 2.0 mol%; B2O3 in an amount greater than or equal to 1.0 mol% and less than or equal to 6.0 mol%; Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 10.0 mol%; as well as K2O in an amount greater than or equal to 0.01 mol% and less than or equal to 1.0 mol%; as well as an optical coating disposed on the first major surface of the glass substrate, the optical coating forming an antireflective surface, wherein the optical coating comprises a scratch-resistant layer and an antireflective coating comprising a plurality of alternating high and low refractive index layers disposed between the scratch-resistant layer and the glass substrate; and wherein the optical coating has a physical thickness of about 50 nm to about 10 microns; wherein the coated glass article exhibits a maximum hardness of about 10 GPa to about 30 GPa measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, as measured by a Berkovich Indenter Hardness Test; and wherein the coated glass article exhibits a retained strength greater than or equal to 250 MPa.

2. The coated glass article of claim 1, wherein the coated glass article exhibits a retained strength of about 250 MPa to about 400 MPa.

3. The coated glass article of any preceding claim, wherein the coated glass article has a failure height greater than or equal to 50 cm as measured on 80 grit sandpaper according to the drop test method.

4. The coated glass article of claim 1 , wherein the coated glass article has a failure height of about 50 cm to about 220 cm as measured on 80 grit sandpaper according to the drop test method.

5. The coated glass article of any one of the preceding claims, wherein the glass substrate has a compressive stress greater than or equal to 500 MPa.

6. The coated glass article of any one of the preceding claims, wherein the glass substrate has a maximum central tension greater than or equal to 20 MPa.

7. The coated glass article of any one of the preceding claims, wherein the glass substrate has a maximum central tension less than or equal to 160 MPa.

8. The coated glass article of any one of the preceding claims, wherein the glass substrate has a depth of layer greater than or equal to 3.0 microns.

9. The coated glass article of any one of the preceding claims, wherein the glass substrate has a depth of layer less than or equal to 12 microns.

10. The coated glass article of any preceding claim, wherein the plurality of alternating high and low refractive index layers comprises at least 3 layers.

11. The coated glass article of any one of the preceding claims, wherein each low refractive index layer comprises a silicon-containing oxide and each high refractive index layer comprises a silicon-containing nitride or a silicon-containing oxynitride.

12. The coated glass article of any one of the preceding claims, wherein the scratch-resistant layer is a high refractive index layer.

13. The coated glass article of any one of the preceding claims, wherein the scratch-resistant layer has a thickness of about 200 nm to about 5000 nm.

14. The coated glass article of any one of the preceding claims, wherein: Each low refractive index layer contains SiO2, Al2O3, GeO2, SiO, AlO x N y 、SiO x N y 、Si u Al v O x N y , at least one of MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3 and CeF3, and Each high refractive index layer contains Si u Al v O x N y , Ta2O5, Nb2O5, AlN, Si3N4, AlO x N y 、SiO x N y 、SiN x 、SiN x H y , at least one of HfO2, TiO2, ZrO2, Y2O3, Al2O3 and MoO3.

15. The coated glass article of any one of the preceding claims, wherein the coated glass article exhibits a double-sided average light transmission greater than or equal to about 92% measured at the antireflective surface over the optical wavelength regime within the range of about 400 nm to about 800 nm.

16. The coated glass article of any preceding claim, wherein the coated glass article exhibits an average single-sided reflectance of less than or equal to 3% over a wavelength range of light from about 410 nm to about 1050 nm.

17. The coated glass article of any preceding claim, wherein the coated glass article exhibits either or both of the following: the article transmittance color coordinates in the (L*, a*, b*) colorimetric system exhibit, at normal incidence, a reference point color shift of less than about 2 measured at the antireflective surface relative to a reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmittance color coordinates of the substrate under an International Commission on Illumination illuminant, and the article reflectance color coordinates in the (L*, a*, b*) colorimetric system exhibit, at normal incidence, a reference point color shift of less than about 5 measured at the antireflective surface relative to a reference point comprising at least one of the color coordinates (a*=0, b*=0), the color coordinates (a*=-2, b*=-2), and the reflectance color coordinates of the substrate under an International Commission on Illumination illuminant, When the reference point is the color coordinate (a*=0, b*=0), the color shift is given by √((a* 制 Products) 2+ (b* products) 2 )definition, When the reference point is the color coordinate (a*=-2, b*=-2), the color shift is given by √((a*product+2) 2 +(b* products+2) 2 ) definition, and When the reference point is the color coordinate of the substrate, the color shift is given by √((a* 制品 -a* substrate)2+(b* product-b* substrate) 2 )definition.

18. The coated glass article of claim 1, wherein the coated glass article exhibits: a single-sided average photopic reflectance of about 10% or less measured at the antireflective surface at near-normal incidence over a wavelength region of light within the range of about 400 nm to about 700 nm; and the article reflectance color coordinates in the (L*, a*, b*) colorimetric system exhibit, for at least one angle of incidence between 0 and 90 degrees, a reference point color shift of greater than about 18 measured at the antireflective surface relative to a reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflectance color coordinates of the substrate, under a Commission Internationale de l'Eclairage illuminant, wherein when the reference point is the color coordinate (a*=0, b*=0), the color shift is defined by √((a*product)²+(b*product)²); and Wherein, when the reference point is the color coordinate of the substrate, the color shift is defined by √((a*product-a*substrate)2+(b*product-b*substrate)2).

19. The coated glass article of claim 1, wherein the coated glass article exhibits either or both of the following: Unilateral photopic average light reflectance of about 12% or greater; and a single-side maximum reflectivity of about 12% or greater measured at the antireflective surface for at least one near-normal angle of incidence over a wavelength region of light within the range of about 400 nm to about 700 nm; and wherein the article exhibits, under an International Commission on Illumination illuminant, for at least one angle of incidence between 0 and 90 degrees, a reference point color shift of greater than 12 relative to a reference point measured at the antireflective surface, the reference point comprising at least one of the color coordinates (a*=0, b*=0) and the reflected color coordinates of the substrate, as measured by the antireflective surface; When the reference point is the color coordinate (a*=0, b*=0), the color shift is given by √((a* 制 Products) 2+ (b* products) 2 ) definition; and When the reference point is the color coordinate of the substrate, the color shift is given by √((a* 制品 -a* 基 board)2+(b*product-b*substrate) 2 )definition.

20. A coated glass article for a mobile display cover comprising: A glass substrate having a composition comprising: SiO2 in an amount greater than or equal to 50.0 mol% and less than or equal to 70.0 mol%, Al2O3 in an amount greater than or equal to 10.0 mol% and less than or equal to 25.0 mol%, and Li2O in an amount greater than or equal to 5.0 mol% and less than or equal to 15.0 mol%, wherein the glass substrate comprises a first major surface and a second major surface, wherein the first major surface and the second major surface are opposite sides of the glass substrate, and wherein the glass substrate comprises: Layer depth greater than or equal to 3 μm; An elastic modulus greater than or equal to 72 GPa; and greater than or equal to 0.7 MPa·m 0.5 fracture toughness; and an optical coating disposed on the first major surface of the glass substrate; and wherein the coated glass article exhibits: Average photopic transmittance greater than 85% and average photopic reflectance less than 8%; a maximum hardness of about 12 GPa to about 30 GPa, measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, as measured by a Bosch Indenter Hardness Test; and Retained strength greater than or equal to 250 MPa.

21. The coated glass article of claim 20, wherein the coated glass article has a retained strength of about 250 MPa to about 400 MPa.

22. The coated glass article of claim 20, wherein the coated glass article has a failure height greater than or equal to 50 cm as measured on 80 grit sandpaper according to the drop test method.

23. The coated glass article of claim 20, wherein the coated glass article has a failure height of greater than or equal to 50 cm to less than or equal to 220 cm as measured on 80 grit sandpaper according to the drop test method.

24. The coated glass article of claims 20 to 23, wherein the composition of the glass substrate further comprises: P2O3 in an amount greater than or equal to 0.0 mol% and less than or equal to 5.0 mol%; B2O3 in an amount greater than or equal to 0.0 mol% and less than or equal to 10.0 mol%; Na2O in an amount greater than or equal to 1.0 mol% and less than or equal to 15.0 mol%; as well as K2O in an amount greater than or equal to 0.0 mol% and less than or equal to 1.0 mol%.

25. The coated glass article of claims 20 to 24, wherein the scratch resistant layer is a high refractive index layer.

26. The coated glass article of claims 20 to 25, wherein the maximum hardness is greater than or equal to 15 MPa and less than or equal to 30 MPa.

27. The coated glass article of claims 20 to 26, wherein the thickness of the scratch-resistant layer is from about 200 nm to about 5000 nm.

28. The coated glass article of claims 20 to 27, wherein the optical coating forms an antireflective surface, the optical coating comprising an antireflective coating and a scratch-resistant layer, the antireflective coating comprising a plurality of alternating high and low refractive index layers; Each low refractive index layer contains SiO2, Al2O3, GeO2, SiO, AlO x N y 、SiO x N y 、Si u Al v O x N y , at least one of MgO, MgAl2O4, MgF2, BaF2, CaF2, DyF3, YbF3, YF3 and CeF3, and Each high refractive index layer contains Si u Al v O x N y , Ta2O5, Nb2O5, AlN, Si3N4, AlO x N y 、SiO x N y 、SiN x 、SiN x H y , at least one of HfO2, TiO2, ZrO2, Y2O3, Al2O3 and MoO3.

29. The coated glass article of claims 20 to 28, wherein the plurality of alternating high and low refractive index layers comprises at least 3 layers.

30. The coated glass article of claims 20 to 27, wherein the optical coating comprises a composition gradient.

31. The coated glass article of claims 20 to 30, wherein the coated glass article exhibits a double-sided average light transmittance greater than or equal to about 92% measured at the antireflective surface over the optical wavelength regime within the range of about 400 nm to about 800 nm.

32. The coated glass article of claims 20-31, wherein the coated glass article exhibits either or both of the following: the article transmittance color coordinates in the (L*, a*, b*) colorimetric system exhibit a reference point color shift of less than about 2 relative to a reference point comprising at least one of the color coordinates (a*=0, b*=0) and the transmittance color coordinates of the substrate under a Commission Internationale de l'Eclairage illuminant at normal incidence, as measured at the antireflective surface; and the article reflectance color coordinates in the (L*, a*, b*) colorimetric system exhibit, at normal incidence, a reference point color shift of less than about 5 relative to a reference point measured at the antireflective surface under a Commission Internationale de Illumination illuminant, the reference point comprising at least one of the color coordinates (a*=0, b*=0), the color coordinates (a*=-2, b*=-2), and the reflectance color coordinates of the substrate, When the reference point is the color coordinate (a*=0, b*=0), the color shift is given by √((a* 制 Products) 2+ (b* products) 2 )definition, When the reference point is the color coordinate (a*=-2, b*=-2), the color shift is given by √((a*product+2) 2 +(b* products+2) 2 ) definition, and When the reference point is the color coordinate of the substrate, the color shift is given by √((a* 制品 -a* substrate)2+(b* product-b* substrate) 2 )definition.

33. The coated glass article of claims 20 to 32, wherein the coated glass article exhibits an average single-sided reflectance of less than or equal to 3% over a wavelength range of light from about 410 nm to about 1050 nm.

34. The coated glass article of claims 20 to 33, wherein the glass substrate has a compressive stress greater than or equal to 500 MPa.

35. The coated glass article of claims 20 to 34, wherein the glass substrate has a maximum central tension greater than or equal to 20 MPa.

36. The coated glass article of claims 20 to 35, wherein the glass substrate has a maximum central tension less than or equal to 160 MPa.

37. A coated glass article comprising: a glass substrate comprising a first major surface and a second major surface, wherein the first major surface and the second major surface are opposite sides of the glass substrate, an optical coating disposed on the first major surface of the glass substrate, the optical coating forming an antireflective surface, wherein the optical coating comprises a scratch-resistant layer and an antireflective coating comprising a plurality of alternating high and low refractive index layers disposed between the scratch-resistant layer and the glass substrate; and wherein the optical coating has a physical thickness of about 50 nm to about 10 microns; wherein the coated glass article exhibits a maximum hardness of about 10 GPa to about 30 GPa measured at an indentation depth of about 600 nm from the antireflective surface of the optical coating, as measured by a Bosch Indenter Hardness Test; and The coated glass article has a failure height of about 50 cm to about 220 cm as measured according to a drop test method on 80 grit garnet sandpaper.

38. The coated glass article of claim 37, wherein the coated glass article exhibits a retained strength greater than or equal to 250 MPa.

39. The coated glass article of claim 37, wherein the coated glass article exhibits a retained strength of about 250 MPa to about 400 MPa.

40. The coated glass article of claims 37 to 39, wherein the glass substrate comprises a glass-ceramic substrate.

41. A consumer electronic product comprising: a housing comprising a front surface, a rear surface, and side surfaces; an electrical component at least partially located within the housing, the electrical component including a controller, a memory, and a display, the display being located on or adjacent the front surface of the housing; and a coated glass article positioned over the display, wherein the coated glass article is according to any one of claims 37 to 40 and 48 to 50.

42. The coated glass article of any one of claims 1 to 19, wherein the composition of the glass substrate further comprises a molar ratio of lithium to sodium (Li2O:Na2O) of greater than, or equal to, 1.2 to less than, or equal to, 2.

0.

43. The coated glass article of any one of claims 1 to 19, wherein the composition of the glass substrate is substantially free of or free of Ta2O5, HfO2, La2O3, and Y2O3.

44. The coated glass article of any one of claims 1 to 19, wherein the composition of the glass substrate comprises: 61-67 mol% SiO2; 12-18 mol% Al2O3; 0.25-1.25mol%P2O5; 2-4 mol% B2O3; 6-9 mol% Li2O; 3-6 mol% Na2O; and 0.1-0.5mol%K2O.

45. The coated glass article of any one of claims 20 to 36, wherein the composition of the glass substrate further comprises: Li2O in an amount greater than, or equal to, 5.0 mol% and less than, or equal to, 10.0 mol%; Na2O in an amount greater than, or equal to, 1.0 mol% and less than, or equal to, 10.0 mol%; and a molar ratio of lithium to sodium (Li2O:Na2O) of greater than, or equal to, 1.2 and less than, or equal to, 2.

0.

46. ​​The coated glass article of any one of claims 20 to 36, wherein the composition of the glass substrate is substantially free or free of Ta2O5, HfO2, La2O3, and Y2O3.

47. The coated glass article of any one of claims 20 to 36, wherein the composition of the glass substrate comprises: 61-67 mol% SiO2; 12-18 mol% Al2O3; 0.25-1.25mol%P2O5; 2-4 mol% B2O3; 6-9 mol% Li2O; 3-6 mol% Na2O; and 0.1-0.5mol%K2O.

48. The coated glass article of any one of claims 37 to 40, wherein the composition of the glass substrate comprises: Li2O in an amount greater than, or equal to, 5.0 mol% and less than, or equal to, 10.0 mol%; Na2O in an amount greater than, or equal to, 1.0 mol% and less than, or equal to, 10.0 mol%; and a molar ratio of lithium to sodium (Li2O:Na2O) of greater than, or equal to, 1.2 and less than, or equal to, 2.

0.

49. The coated glass article of any one of claims 37 to 40, wherein the composition of the glass substrate is essentially free of or free of Ta2O5, HfO2, La2O3, and Y2O3.

50. The coated glass article of any one of claims 37 to 40, wherein the composition of the glass substrate comprises: 61-67 mol% SiO2; 12-18 mol% Al2O3; 0.25-1.25mol%P2O5; 2-4 mol% B2O3; 6-9 mol% Li2O; 3-6 mol% Na2O; and 0.1-0.5mol%K2O.

51. A consumer electronic product comprising: a housing comprising a front surface, a rear surface, and side surfaces; an electrical component at least partially located within the housing, the electrical component including a controller, a memory, and a display, the display being located on or adjacent the front surface of the housing; and a coated glass article positioned over the display, The coated glass article is according to any one of claims 1 to 19 and 42 to 44.

52. A consumer electronic product comprising: a housing comprising a front surface, a rear surface, and side surfaces; an electrical component at least partially located within the housing, the electrical component including a controller, a memory, and a display, the display being located on or adjacent the front surface of the housing; and a coated glass article positioned over the display, The coated glass article is according to any one of claims 20 to 36 and 45 to 47.

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